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2. Molybdenum and Tungsten
CoordinutionChemistry Reviews, 90 (1988) 29-109 ElsevierScience PublishereB.V.,Amsterdam-PrintedinTheNetherlanda
2.
AND
MX.XBDENun
29
TUNGSTEN+
R. COLTON
CONTENTS
Introduction . . . . . . . . . . . . . . . . . . * . . . . . . . ...* . . . . . * . Molybdenun(V1) and Tungsten(V1) .......... 2.1 . . . . . Halides and halo complexes ......... 2.1.1 . . . . 2.1.2 Oxides, rolybdates and tungstates ..... . . . . Monomeric 0x0 complexes .......... 2.1.3 . . . . 2.1.4 Dimeric and polyaeric 0x0 complexes .... Coaplexes with oxygen donor ligands .... 2.1.5 sulphur donor 2.1.6 Thioaolybdates, thiotungstates and complexes .................. . . . . . . . Homonuclear polyanions ........... . . . 2.1.7 . . . . . . . 2.1.8 Heteronuclear polyanions .......... Coaplexes with nitrogen and phosphorus donor 1 igands 2.1.9 . . . . Molybdenum(V) and Tungsten(V) ........... 2.2 2.2.1 Halides and halo coaplexes ......... . . . . Monomeric 0x0 complexes .......... . . . . 2.2.2 . . . . 2.2.3 U-oxo, Lr-sulphido complexes ........ Complexes with nitrogen donor ligands ... . . . . 2.2.4 . . . . Molybdenur(IV) and Tungsten(IV) .......... 2.3 2.3.1 Halides and halo coaplexes ......... . . . Complexes with oxygen donor ligands .... . . . . 2.3.2 . . . . 2.3.3 Coaplexea with sulphur donor ligands .... 2.3.4 Complexes with nitrogen and phosphorus donor 1 igands 2.3.5 Complexes with metal-carbon bonds ..... . . . . . . . . 2.4 Molybdenun(III) and Tungsten(II1) ......... Molybdenum(I1) and Tungsten(II) .......... . . . . 2.5 2.6 Molybdenum(O) and Tungsten(O) ........... Metal-aetal Bonded Species . . . . . . . . ._~~. .. . ._ . . . . . _~~~. . . 2.7 Triple bonded species of molybdenua(III1 and tungsten (III) 2.7.1 2.7.2 Quadruple bonded species of molybdenur(I1) and tungsten(II) 2.7.3 Hexwric species . . . . . . . . . . . . . . . . . . . . 2.7.4 Other cluster species . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . l
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29 30 30 35 37 46 49 51 54 55 57 62 62 65 66 70 72 72 73 76 78 80 82 87 88 89 89 97 101 101 104 104
INTRODIJCTION The inorganic
review and
on molybdenum coordination
Chemical
Abstracts,
1985
some
and
Organometallic included
in the
chemistry, review,
tungsten
chemistry
Volumes
published
and
102
towards
and
103.
the
end
including but
of
reference
chemistry
the
elements
Thus of
this
most
1984
carbonyl is made
which of
will
+ HO REF'llINT8 AVAILABLE
0010~8546/S8/$28.35
@198SElsevier
SciencePubliahersB.V.
deals
with
was
cited
in
the work
published
be reviewed.
chemistry, to some
year
is not papers
formally
of general
the
in
30
interest. The year_
arrangement
The
oxidation
state
determined
by
are
of
2.1
MOLYBDENUM(V1)
2.1.1
HaZides
of
donor the
apply
to
both
AND
ha20
fields
M02F2
was
good
the
gas
The
measurements
(M
and
at
mean
= Cr,Mo,W). WF6
reacts
and
rate
of
were
MOF4
(MO).
Ba2CM02/2 units_ IR
0
have
of
1
2-
were
B4
being
which
are
separated almost c73.
mono-
a
and
the
been
reaction
with
IR,
the
the
ordering the
M
been
is
is
compounds
used
where
calculated
and
for
experimental
MF6 data
-, NO -, SF - and SF - in 2 5 3 6 ratios have been determined. of
WE6
is
mass
volatility
difficult
single
BC13
small of to
After
x
lo4
and
as
showed
single
the
tungsten(VI)
peroxo
in
and
The
formation
l-96
+
19F
034
SF02
Compounds
NMR
The
studies
crystals
(W)
to the
[41. or
a
anion
containing All
the
H202
and
tungsten
species
constants 3-52
as
be linked
predominant
x 1012<
[31_
C14Mo=NTeF5_
of
and
F4M=NTeF5
solutions
the
MF6
reaction
electrode.
and
of SiF4
compounds
chains
selective group
the
gave
spectral
derivatives.
7.15
extraction
insoluble.
by
by
of
+ H2NTeF5
prepared
fluoride
interaction
prepared
2Me3SiF
been
a
trifluoro
chlorination
by
NO
affinity
by
is
studies
using
104(01<
negligibly
The
I-,
-
by have
formation
studied
x
have
branching
obtained
have
+ MF6
compounds
complex
4.84
symbol
calculated
electron
method
group
compound,
contained
the
ranges
the
Crystallographic
been
complexes
Br-,
and the
vibration
F IF with the structure containing 2 2 2 and Raman spectra were reported [51.
Fluoro F-
the
complexes
The
last is
tungsten.
between
Cl-,
are
characterized
Ba2[M03F4] powder
F-,
that
pure
CNTeF5
molybdenum
compounds
of
agreement
with
advantage
the
the
and
for
material
state
ligand
type.
review
of
TUNGSTENtVI)
coefficients
2Me3SiN(H)TeF5
With
the
121.
The
containing
mixed
molybdenum
of
oxidation
ligand
amplitudes
indicated
yields
120°C.
With
that
presentation
each
dominant
The
El].
3.3(+0_04,-0.2)eV
within
atom.
to
the
comptexes
phase
High
and
of
similar
ordering
metals
type
and
and
the
is
of
terms
in
comments
Force
material
criterion
the
described
similar
of
primary
observed
lie
in
with
x 1O1'
the B2
and
[61_ W03
and
separate. with
Et20
filtration,
tungstates
gives
It
been
has
since
now WOC14
evaporation
is
mixtures found very of
the
of
that
WOC14
they
soluble solvent
and
can
and
W02C12
be
easily
W02C12
gave
pure
is WOC14
31 Interaction solution
gave
crystals
of
structure
of either
a mixture
the
of
latter
MoC15
complex
the anion
or MoCI4
of MoC13(N3S2) were
is shown
in
with
and
(NSC1>3
in dichloromethane
CN(SC~)~ICMOCI~(NSC~>~.
characterized
by X-ray
Black
diffraction
and
the
(1).
S-Cl
i’,N
~1,
/ (1)
MO
I’
’
Cl
Cl
Cl
Bond
distances
are
MO-N
= 1.75
N)
= 2.47
MO-Cl
N-S
= 1.59
S-Cl
MO-Cl(trans
The
MO-N-S WClS
dimeric
unit and
with
(PPh4)CW2NCl10
is linear
(Me3Sij3N chloro
bridges.
1 which
I
and
react
was
Cl,
the bond to give However,
shown
/Cl
Cl
N--/W\ Cl
double
on
the basis
with
(PPh4)C1
diffraction
Cl,
Cl
suggested
which
on reactton
by X-ray
A"\
Cl
lengths W2NC19
= 2.32-2.37 = 2.038
to have
bonding of
(81.
IR data
is
it gives
the
structure
-
,Cl
c1 Cl I
(2)
(R)_
32 Bond
distances
are
W=N z 1.79(Z),
N)
=
2_367(6),
N)
=
2.276(6)-Z-316(6)8
w-cl(tnzns w-cl(cis
The
W-N-W
unit
solution
of
is
linear
and
(PPh4)[W2NCl101
the in
(PPh4>2[W3N2C1141_CH2C12_CC14
remarkable
CH2C12 by
are
almost
structure
linear
corresponding eclipsed
but
to
of
the
configuration
I
and
double
slowly
CC14
forms
bonding
[9].
crystals
A
of
reaction
[W3N2CL14]2-
anion
in
asymmetric double
suggest
this
compound
nitrido
bonds.
+ WC16
is
bridges
The
shown
with
equatorial
WC14
in
W-N
(3)_
bond
units
There
lengths are
in
the
[lo].
Cl,
Cl
and
lengths
-
the
highly
single
2.399(6)
bond
2[W2NCL101-
The
l-88(2)
/Cl
Cl,
,W\
N
Cl,
N
,W\
Cl
Cl
,,I
Cl
Cl
2-
/Cl
C1
,W,
Cl
Cl
(3)
Average
bond
distances
W=N W-Cl(trans
The
of
isolated W-N-C linkage
as unit
NEt3
its is
[ll].
= 1.835
N)
interaction
quantities
are
= 2.40
of led
(AsPh4)'
almost
and
WC13N to
the
(CF
formation
salt.
linear
W-N
=
2-065
N)
=
2-312
W-Cl(c$s
and
The
) CO 32 of
in
structure
there
may
MeCN
C(WC15j2 of be
the
triple
in
the
presence
anion bond
is
of
12-
p-NC(CF3>2N
shown
character
catalytic
which in
(4).
in
the
was The W-N
33
2-
l,i’,
1 C
C
Cl
/;1
(4)
c1
Cl
Bond
distances
W-Cl(trans
Two
groups
groups
the
Both
structure is shown double
[12,13]
have
[MC13(N3S2)12
and
ligand.
= 1.743(15)
in
to IR data,
tungsten
the
reported
are made
compounds
of
C-N w-cl(&a
N) = z-437(7)
According
(NSCl13.
CF3
are
W=N
complexes
A
CF3
tungsten
WN3S2
dark
compound unit
(AsPh4)Cl was
cyclothiazen,
through to give
determined
is planar
of MoNC13
compound
is associated
with
brown
interactions
the molybdenum
complex react
that
by the
= 1.415(22)
N) = 2.304(9)-2,326(8)2
and
is bridged
the Y-nitrogens
cl21
the W-N
by X-ray distances
Cl
s/
N,l,cl
N
\
(5)
S-N/!\
I
Cl Cl
I-
Bond
distances
are
W-N W-Cl(trcms
N)
= 1.85tav) = 2.44
W-Cl(cis
N-S
= 1.54-l-61
N)
= 2,398(av)
with
by chloro
(AsPh4)[MC14(N3S2)l
bonds.
r-
[N3S2]-,
and WCC14
of
the and
diffraction correspond
the and to
34 Reaction crystals
between
of
(AsPh4)[WClq(N3S2)1
(AsPh4[WOC1_,(0S2N2)] determination The
WNSNSO
(AsPh4)[C14W
ring
the is
could
latter
planar
Bu]
and
described
which
on
C
be
the
above
separated
compound and
S4N4
bond
and by
revealed W-N
in
the length
dichloromethane red
hand
crystals
brown
of
picking_
A
stereochemistry corresponds
gave
structure shown
to
in
a double
bond
c143.
Cl
O\\l/
c/j\
(6)
Cl
Bond
distances
are
W-N
=
l-833(4)
w-0
=
l-699(3)
N)
=
2.406(l)
W-cl(trans
Mo02C12
reacts
with
(7)
=
2-288(3)
N)
=
2.381(1)2
diisopropyL~N,N-diethylcarbamyl)methylenephosphate, to
(iPrO)2P(0)CH2C(O)NEt2,
w-cl(cis
w-o
give
the
1:l
adduct
whose
structure
c151.
Cl
,/i’\ \
(7)
Cl
LPrO
-
/“ OiPr
’
I"
yCANEt2
is
shown
(6).
in
Average
bond
distances
are
Ma=0
=
1.682
MO-Cl
=
2-3802
MO-O
N,N-dichlorophenylsulphonamide give
polymeric
monomeric
=
reacts
[(PhS02N)2WC12]
which
x
the
(PhS02N)2WC12(MeCN)2
on
2.233
with
W(CO>6
in
dissolution
structure
of
in
which
refluxing
MeCN
is
gave
shown
CC14
to
crystals
in
(8)
of
[161.
0
\“/
MeCN
\
/“\
MeCN
H-0 H
N-S
Ph
(8) Ph
/
N-S
\x 0
Cl
Average
bond
distances
are
W-Ncnitrene) W-Cl
The
W-N(nitrene)
The by
standard
solution
of
laser
Raman
W30g
and
=
2.3352
= 2.226
surprisingly
long.
and tungstates
to
be
cl?'].
W4012
spectrum
W-N(MeCN)
is
with
of
W03
of
Moo3
of
W03_2H20
-(1430.1+1.0) The
technique
W206 has
and
sublimation
with
been
mass and
and
W308
have
been
determined
-(1133.0*1.0)kJmol-1
of
W03
spectral
reported
W03.H20
has
been
analysis.
present and
as
minor
assigned
investigated
The
vapour
species on
the
by consists
[18].
basis
of
The C3v
C19J.
Co-condensation and
1.775
enthalpies
298.15K
effusion
mainly
symmetry
molar
at
Knudsen
=
distance
calorimetry
respectively the
bond
Oxides, mob~.b&tes
2.1.2
o
photolysis
of
the
slurry
vapour
with
of
condensate
the
MeOH
at in
-196OC MeOH
gives under
Mo205(0Me)2.2MeOH 02
gave
(Me012CH2
36 in a slow new
catalytic
form
It has biochemical bound
been
Manganese
products
depending
different
the hydrates
diffraction (9)
and
with
water
H20
gave
a
be a viable of
probe and
[M004]~-
for
[MoS412-
by precipitation
the
At pH
solution.
the
from
into
other
7-8
of tetrahedral
tetrahedra
share
aqueous more
the product molybdate
corners
obtained
and
with
four
to manganese.
At higher
been
by annealing
coordinated
solution.
crystalline
temperatures
to a-MnMoO 4 c221.
(W:Na:Li
revealed
slight
may
spectra
at 60-100°C
of Na6LL2[W20101
Lip0
NMR
consists
in which
transform
study
prepared
transformed
the pH of
with
spectroscopy
the 95Mo
its structure
crystals
of wo 3, Nap0
of MOO., with
[211_
were
was
units
octahedra
Single
in
albumin
upon
and
co-condensation
MO NMR
by examining
serum
Mn(I1)
95
that
molybdates
MnMoO 4.H20
all
shown
precipitate
octahedral
Similar
[20].
systems
to bovine
The yellow
was
conversion.
of Mo03_2H20
have
= 1:3:1)
mixtures
at 840°C for 60 days. An X-ray 8anions with the structure
[W2010]
discrete
asymmetry
prepared
in the 0x0
bridges
shown
[23].
o\i,“\i/o 0
+lo/+o
6 )
0
0
Bond
distances
are
w=O
The
correlation
between
phosphate
tungsten
estimates
intermediate
physical
bronzes
measurements
A new
which
The
structural
columns
of
Relationships
the ReO 3 type
Potassium to prepare
and
brown
groups.
length
has
valence
6 for
the valences.
d-electron tungsten
framework
the mono
by
has
mixed
indicate
been
valence
2-1642
5 and
extending
bronzes
and
= 2.024,
other
diphosphate
with
vapour
tungsten
bond
between
reddish
synthesized.
W-MO
I 1.809-1.916
can
along bronzes
directly
this method.
applied
oxFdes
This
with
Attack
on
and
has
as 2 x 2 W06 connected
are discussed W03
led to with
[241.
CS[P~WSO~~]
COO11
to
is in accord
delocalization
be described
phosphate
reacted
tungsten
bronze
indefinitely
been
crystals
the oxide
been octahedral by P207 C251,
in an attempt was
extensive,
37 but
only
limited
(200-900°C The
for
compound O-25-168h)
interaction
following
in
observed
under
the
conditions
employed
R3SiOH
(R
=
Ph,'Bu)
with
the
2-
[Mo2071
ion
gave
the
reaction
structural
as
was
1261.
of
2R3si0~
A
formation
-
Z(NBU~)CR~SIOMOO~I
+ H~O
\ IPhPh
study
(10)
(NBU~I~CMO~O~~
+
of
(271.
the
salt
with
R
=
Ph
confirmed
the
structure
of
the
anion
Si-0
-
/
Ph
Bond
distances
are
Mo=O
2-
also
cMo2C71
in
2.1.3
Monomeric
has
(10).
appeared
monomeric, reactions a
different
a
It
and are
seven
is
very
MO&
=
MeCN
was
structure
1.884(4)x
to
give
followed of
similar 2.154(6),
of
coordinate all
0x0
the
progressively by
visible
final
to that MO-~0
at
between group
to lower
be pHls
tungstate 1
using
cryoscopic
and H
complexes.
dimeric
and
of =
absorption,
product its
analogue
l-881(7)2
C28l.
NMR
in of
molybdenum
the
metal
chemistry
and
includes
the
Mo(VI).
and and At
species
thiomalic l3 C
states of
tungstate
0x0
structures
oxidation
complexes
between
polarimetric,
thought
but
sequence The
cover%
number
by are
reaction
of
formation
investigated observed
in
(Me3Sij2S
=
0x0 comptexea
review
of
Complex
with
distances
C293_
structures
MO-PO
determined
Bond
general
1.699Cav)
spectroscopies_ was
shown
A
reacts The
[MOO 3_xSx(OSiMe3)l-. 17 95 MO and 0 NMR [MoS3(OSiMe3)]-
=
acid
Z(-)malic acid 1 H NMR methods. high
pH
(>7)
predominate at
spectroscopies.
pH
has All the
[30], 2-7 A
been
have number
the
stable
species complex
is
Similar been of
conducted 0x0
by
38 complexes
containing
Reaction
of
two
thiomalate
Mo02(acac)2
ligands
with
a
were
series
of
identified
[31].
2a-hydroxybenzimidazoles
(L)
(11)
Y
(11)
gave H
Mo02L2.
and
the
Z
A
= Ph
alkoxy
crystal
showed
structure the
imino nitrogens trans 95 MO NMR spectra were previously
ligand
The
oxygen.
and
two
to
to
the
&s
recorded
oxygen
for
donor
oxygen
two
ccs
and
0x0
2.059(4), trans
one
atoms
to
0x0
the
different
=
Bond
group.
compounds
appropriate
by
reaction
The
sterically LN(OHj2 with
respectively. (13).
2R2NOH
(R
(mixed
with
separation
complexes
and
its 2
183W
structures
dmso of
case
= Et,bz)
-
IR
both
two
In
this
=
trans
the
case to
1.938(S) in
force
prepared
from
in
+
W02(R2N0)2
the
and each
case
the
the
W02C12
by
spectra
very
shifts
of
the NEt3
2(Et3NH)C1
were
chromatography similar
were
and
presence
complexes
achieved
to
prepared and
those
recorded
of
their
[343.
-diphenyl-2-hydroxyethyl)-
LN(SH)2
have
Mo02(LN02)(dmso)
compounds
within
The
[331_ were
2,6-bis(2,2'
give
the
given.
fall
distances
effects
monooxomonothio)
analogue to
steric
and
with
are
MO-O
longer
=
with
Mo02L2
dichloromethane
chemical
ligands
sulphur in
this
in
1.70(av), the
that
was
gave
their
demandtng and
Mo02(acac) The
2NEt3
=
they
Mo(VI)
Y
with
not
structure.
ligands
with
in
+
and
analogues
pyridine,
and
+
B2S3
recrystallization.
(12)
in
different
Mo=O
suggested
arrangement
dithio
with
molybdenum
reacted
was
N,N-dialkylhydroxylamine
corresponding
The
It
are
2.325(5>%
c~s-WO~(R~NO)~
W02C12
The
and
a
= H,
nitrogen
were
studies
X
octahedral
and of
with
imino
is
complexes
Similar
different
the
distances
complexes
[32].
distances
2.142(5)
structural
The
from
Bond
the
dioxo
revealed
nitrogen
groups.
MO-N
all
compound
molybdenum
groups.
C&Y
the
through
about
for
range
on
chelating
0x0
2-o-hydroxyphenylbenzimidazoles one
be
stereochemistry
established
nitrogen
determination
were
been and
determined
prepared
and
Mo02(LNS2) and
are
shown
in
39
Ph \
0SMe2
/\ Ph
Ph
Ph
Ph
\/
(13)
Ph
Ph
Bond
distances
are
Mo02(LNOp)(dmso) MO=*
1.705(4)
Ma-0
1.902(3)
l-694(6)
MO-S
The
2.415(2)
MO-N
2_417(4)
MO-O(dmso)
2.382(7)R
bond
Mo02(LNS2)
to dmeo
in Mo02(LN02)(dmso)
2.244(7)
is long,
implying
lability.
MOO~(I.NS~)
is
the
first
five
coordinate
trigonal
bipyramidal,
reported
[351_
The
complexes
molybdoenzymes 0x0
system
Mo02(LNS2)
to and
which
turns
and
Mo02(LNS2) from
over
the
Schiff
base
MoO(LNS2)
reacts
coordinating ligands
AA
thought
to be
compounds
(AA
have
salicylaldehyde A
where
and
is the
-
(14)derived
to form This
compounds
models
to yield
coupled
for
are
0x0
MoO(LNS2)
to produce
Me2S
+ PPh30
from
salicylaldehyde
reported
Mo02(sal-shz)(H20) compound
en etc)
blpy,
coordinate
on
to give
containing
transfer
and
and
with
with
the
ligand
bidentate
nitrogen
MOO of
(Sal-shz)(AA) which 2 IR studies [371. Very
the Schiff
base
derived
are similar
from
Schiff
Mo02(sap)(im1d) base
have
been
synthesized
(15).
(15) C=N H
compounds
Mo02(sap)(EtOH)
were
prepared
followed
PPh30.
a catalytic
OH
The
also
C381.
complexes
tridentate
reacts
the basis
benzoylhydrazide
of octahedral
series
H2sap
been
useful
PPh3
been
is approximately
H
O-&O_
= phen, seven
geometry of both
are
with
have
+ PPh3
(Sal-shz)
is known
through
the
reaction
H
SalFcylhydrazide
and
properties
substrates
Me2SO
The
complex
Electrochemical
[361.
transfers
Mo(V1)
/
from
Mo02(acacj2
by reaction
with
and H2sap
imidazole
in EtOH
[3gl.
to give
41 It has reduction rapidly
been
shown
of N02gives and
reduction
of MoO2(dtc)2
N20
reports
both
MoO2(Et2dtc)2
by HCOOH
Mo02(dtc)2
MoO(dtcj2
Two
that
to N20
and
The
respectively. by HCOOH
have
Both
[N,O,]-.
appeared
and
The
in dmf,
rate
MoO(Et2dtc)2
reaction
products
react
determining
catalyze
of MoO(dtcj2 with
step
HCOOH
in the
the
with
N02-
to give
is
cycle
the
[403_
on
the preparation
2,3,8,9-dibenzo-1,4,7,lO_tetrathiadacane
of MoO2cdttd)
where
dttdH2
is
(16).
(16)
Reaction [411
of Mo02(acac)2
while
reaction
Mo02(dttd) the
pure
and
the
complex.
structure
in thf
dttdH2
Mo203(dttd)2
Mo(VI)
revealed
with
of dttdH2
with [42].
in
temperature
diffraction (17) with
in MeOH
oxidation
However,
An X-ray shown
at room
(NB~,>,[M080263
of
study
the
this
on poor
thiolates
gave
gave
Mo02(dttd)
a mixture
mixture
yielded
quality
trana
of
crystals
to one
another
\9 s\i./o ’
(s/j”\o
(17)
s
b b
(MO-S with
much
complex scale, and
and
= 2.402(7)g(av)) longer
shows but
on
the product
species
MO-S
MoO(dttd)Cl.
of
time
CMoO(dttd)CllThe
&rans
2.687(6)x
one-electron
coulometric
was
thioethers
distances
a reversible the
the
to each
C423.
reduction
In the on
a two-electron
which
could
&S
0x0
presence
reduction
be oxidized
properties
the
of
to the
these
and
groups
of NH4Cl
the voltamnetric
scale
electrochemical
of
the
time
was
observed
EPR
active
related
42
complexes site
were
of
the
described
molybdenum
CataLytic MoO~(L-L)~ alkyl
and
air
or
cofactor oxidation
Mo~O~(L-L)~
ester,
related
of
the
of
benzil
in
(L-L
cysteine-n-
catalyst
the
behaviour
of
the
molybdenum
binding
[423.
complexes
S-deprotonated
deactivation
to
dmf =
occurs
Et2dtc,
decylamide)
occurred
due
to
in
the
presence
S-deprotonated but
in
formation
of cysteine
most
cases 2+ [Mo2043
of
a
slow
species
c431. Compounds
of
the
1-dithiocarboxylic
type
acids
MoO~(L-R)~ (18)
were
(w h ere
L-R
prepared
by
=
2-(alkylamino)cyclopent-ene-
reacting
I-IL-R with
Mo02(acac)2.
R
C-3)
\ /
H I I
;_
I
/ HS
Mo02(L-RI2 to
complexes
coordinate
coordinate. examples
With of
Mo(IV)
very
has
Moo3
rare
to
give
atoms,
reduction
MoOCL~(L-R)~. so
the
occurs
paramagnetic
(u
to
=
The
chloro give
ligand
is
derivatives
Mo(L-R)~
2.35-2.77BM)
which
eight
thought
are
seven
are
coordinate
shown
heating,
prepared
to
be
it
loses
by
the
of
water
Mo02(02).H20
on
a mole
action the
of
basis and
H202 of
half
on
IR,
the
UV
a mole
metal
and of
or
on
thermal
O2
to
give
[451. and
Moo3 excess
thf
crystals the
HCl
peroxide',
been On
HCl
sulphur
c441.
'Molybdenum
studies,
with
both
excess
the
systems
MoO3,
react
through
thf
were
exposed
to
of
of by
pentagonal bonded
any
X-ray
strong
bipyramidal
After
crystallized
addition in
and
light.
77K
and
Addition
the out
oxidizing
diffraction
which of
malonic
presence at
pH
is
of
of
3.
Malic
acid
for to
a
H202, also
resulting
water
and
Fn
peroxo
colourless the gave
of
complex the
The
groups
structure to
peroxo
be
in
in was
a
groups
are
linkages_
solution
of
Moo3
in
K2CMo0(02)2(ox)j oxalato
with
gave
peroxo
the
atom
[46].
stirred
18-crown-6
but
molybdenum (19)
Mo(VI)
solid
formation
surprising, the
shown
usual acid
is
showed as
excess
the
The agent
which
environment
asymmetrically,
solution
air
at
[MoO(02)2(H20)2](18-crown-6)_H20_
absence
confirmed
co-condensed
complex
KOH
gradually and
the
43
Bond
distances
are
MO-O Mo-H2O(ax)
mechanism
of
confirmed
the
before is
but
the
to
donor
structure and
The
of
data
for
new (19)
not
the
the
The
compounds
X-ray
the
diffraction
structure
has
accurate.
The
structure
replacing
the
aquo
groups
with are
the
again
given
0x0
and
slightly has
1_716(7)
one
M-0(02)
1.940(1),1.960(l)
1.935(6>,1.966(6>(av)
M-O(ax)
2.269(l)
Z-245(6)
M-O(eq)
2.051(l)
2.033(6)x
K2[MoO(02>2(C6H607>]_l/2H202_3H20
the
group
of
and
the
interesting
anion
feature
citric
is
has
acid
shown
in
the
in (20)
the
the
anion
so
the
carboxylate [471_
determined
The C481
below.
1.676(l)
K2[Mo04]
of
ligands,
been
M=O
of
determined
asymmetric
also
K2[WO(02)2(ox)l
complex
study been
more
K2[WO(02>,(ox)~ are
1_920(4)
group
bipyramidal
peroxo
An
complex;
is
isostructural
both
the
oxalato
pentagonal
1_900(4),
= 2.084%
understood_
of
determination
axial.
=
K2[Mo0(02)2(ox)1
interaction
is
been
isolated
presence
of
similar
coordination
of
to the
from
excess
the
the
H202_
oxalato
deprotonated
The
complexes hydroxy
C491. The
proline
interaction etc)
in
of
the
MoO(O~)~(HAA>(H~O). derivatives discussed the
MO-O(02) Mo(H20)(eq)
is
with
is
stereochemistry but
2.325
reaction
stereochemistry oxygen
l-647(4)
=
identification
this
similar
=
form
above. their
presence Crystal
revealed
of
Moo3
very
The
amino
Zwitterions
and of
amino H202
structure similar acids as
acids gave
shown
(=
complexes
in
on
which
coordinated (21)
glycine, of
determinations
structures are
HAA
are in
for
the the
or-alanine, type glycine
closely
a monodentate the
valine,
glycine
and
related fashion complex.
proline to
those in
0
“7Jl/”
1. I / / OI"+O
C02H
’
0'
0
CH
2
.C
\C
YC C02H
Bond
distances
H2
II
0
are Mo=O
Mo-O(ax)
=
l-655(8)
MO-0(02)
= l-926(9),
=
2.220(8)
Mo-O(eq)
=
l-975(8)
2.011(7)%
H II
H \I/ N
0
\
0
C4
2I
\
II/O\
0 \
0
M*
o-
\/
(21)
0 OH2
Bond
distances
are
Mo=O MO-0(H20)
=
1,680(l)
=
2.346(1)2
MO-O(O2)
=
1.932(1)-1.962(l)
45 The
peroxo
above
groups
the
are
pentagonal
only
~is-[Mo02(pip-N0)21 its
substituted
in solution methods.
showed
reacts
their
and
in
to give
been
confi.rmed
to be
with by
atom
is 0,362
the
(catechol,
chelated
a structural
in a pentagonal
H2cat)
and
compounds_ They are rigid 1 H and 13C NMR using
investigated
symmetry
Cs
atom
the molybdenum
[SO].
MoO(pip-NO)2(cat)
have
this
was
and
group
1,2-dihydroxybenzene
inferred
the molybdenum
shown
the 0x0
with
structures
results
plane
asynxsetric
towards
derivatives
and
The
the mirror
slightly
plane
catechol
lying
determination
bipyramidal
in
which
environment
as
(22).
0
II/O\ I\
CT
-N
;\MO
N’
G \ 0 0
0
Bond
distances
I
are
Mo-O(cat)
MO-O = 1.688(6) MO-O
The
Mo-O(cat)
trans
bond
to the A
0x0
series
NCS,NCO,N3)
of
have
distances
group
are
the
types
observed complexes an inverse chemicals
g5MO
NMR
of
the
prepared
spectra
[MoL(dtc)3]"+
of
a range
halogen shifts
type
C521
of
+ 2XX
is no
apparent
lengthening
180ppm
to
WO(OR)2X2
seven
+ 2KCl
coordinate X = Cl,Br)
complexes have
1+ and MoOX2(dtc12 3 the MoOX2(dtc)2 compounds
of
been
CMoO(dtc)
with
nitrido
low
of
(2. = O,N,NPh; The
x=
(R = Me,Et,iPr,nBu;
reaction
number
13Oppm The
the
-
solution_ about
WO(OR)2X2
by
a Large
dependence. about
so there
same,
and MoLX2(dtc12
in dichloromethane span
the
= 2_123(8)'A(av)
c511.
compounds been
= 2.014(5)
MO-N
= 1.971(7)
WO(OR>2C12
The
w.4)
complexes
frequency
of
MoN(dtc)3
their
0x0
have
analogues
showing
95Mo c531.
46 Dimeric
2.1.4
There and
on
with
Raman
comphxes
and
FTIR
groups
Both
types
interact
with
As change
the
with
suggested
that
diagnostic
of
is
crystal
determined. in
is
very
the
configuration
of
the
of
for angle
from
/o\+N ’
structure
Mo(VI)
increases
species
identities their
their
g5Mo
NMR 0x0
on
0x0
groups
to
that The
1983. the
[Ma2051
tridentate
gave showed
/ \/ M
/ MO -
0
is
oxygen
compound
the
stereochemistry
The
angle
The sequence
Mo=O
=
l-713(8)
MO-O
=
2.018(6)
=
2.353(7),
at
the
in
the
bridging solid
interaction of
MO(W)
been
a facia2 C563_ (HL)
\ MO
Mo205L2(dmf)21.5H20.
/
shown
in
0
(23).
\
3 -
\
(23)
A
\
N
\
/
followed
/
are
Mo-O(dmf)
asymmetric
C551_
adopts
0
0
[541_
core
147.0(5)O
the
-
0
0
monomeric
for
has
ligand
dmf
dmf
alumina,
groups
I
0
distances
the
2-o-hydroxyphenylbenzimidazole
dmf/H20
monodentate onto
120ppm 2+
species
Mo205(Me2CH2CH2N(H)CH2C(Me)2S)2
bridging
with
determination
of
two
while
about
solution
bridged
oxalato
at
bridged
0x0
with
monodentate signal
in
absorption
I
Bond
oxalates
dimeric
monomeric
via
via a
the
Mo205(Me2NCH2CH2N(H>CH2CH2S)2
at
Mo02(acacj2
recrystallization
to
a mono
similar
review
and
Reaction
surface
structure
It
described
the
of
pH
their
surface
interact been
study the
retain
has
complexes
crystal
0x0
alumina.
oxalato
dimers
The
a onto
groups.
It
by
been
chelated
species
0x0
has
absorption
oxalato the
and poZynerZc
reactions
(PPh4>2fMo205(SC6H40)21
=
1.855(8),
MO-N
=
2.204(av)
oxygen
is
165_4O
and
the
w h ose
the
bridge
is
distinctly
c571.
(PPh4>2cMoOS3(CuCl)31
but
l-906(8)
2.390(7)x
state
of
MO-u0
only
with
product
structure
so is
far
shown
KSPh
in
MeCN
characterized in
(24).
gave is
a complex
47
MO
S-
Bond
distances
u-O(ligand) highly
= 2.117(2),
bridges
oxygenated
Interaction L-valine, MOTORS
S
MO -
= 1.705(2)(w)
MO-uO(ligand)
this
-
0
are
Mo=O
The
-
are
DL-valine which
asysnnetric-
species
of Na2CMo04] etc) are
2.482(2)
It
is copper with
in H20 thought
amfno
at pH
MO-u0
catalyzed acids
to have
the
\
that
gave
the
structure
!o/o\ll/,o O\
c-/o
OH
I CH(R)
I NH3+
of
(25)
L-alanine,
complexes
(25)
0
/\
formation
(LH = glycine,
MO HO
the
[58].
(LH)
2 at 80°C
0 0
thought
is
= 1_929(2)'A
in which
the
amino
48 acid
in the Zwitterion The
from
compound
the mother
be made
more
form
bridges
K6~W4Og(O2>6(CO3>1_6H20 liquor
was
in the preparation
rationally
from
showed
a new
crystallography
the metal
atoms
c593.
first
obtained
as a by-product
of K2[W0(02)2(ox)],
and H202 K2C03 tetratungstate(V1)
but
[W0412-,
in water,
type
as shown
it can
also
X-ray in
(26).
0
-0
0
0
\
\/
\
“c
O
/
,4,0vL
O\,
/
\oOo’ll\
o(i
0,
I/O
G”,
0
\
(26)
o//7(---
“\ A\
o-
Average
bond
distances
w-0
The
structure
are
seven
have and
tungsten
only all
peroxo)
oxygen
Reaction in acidified
= l-95(5)
W-O(eq)
= l-98(318
of
a parallelogram
bridged
group
atoms as
W-O(02~
= 2.21(3)
tungsten
peroxo
tungsten
= l-70(41
consists atoms
coordtnate; one
an 0x0
black
X-ray in
short all
units bridging
MO-N
suggest
1 and W2
group
3 which
distance, multiple
are
and W4 have axial
atoms All
with
the
bridged two
together
with
crystals
(NHEt3)2~Mo204(OMe>(NNPh)21~
bidentate
tungsten ligand.
by
peroxo
with
two
tungsten the
atoms
carbonate
groups
another
each
(not
[60]_
yielded
structure
of
carbonato
Atoms
tetranuclear &s-M~(NNP~)~
the
atoms
each.
have
shown
by
of Mo02(butane-2,3-diolatej2 MeOH
0
are
W-O(ax>
opposite
0
shown
bridged groups.
the N-N bond
diffraction
Mol-Mo3
distance
order
of empirical
(27).The
by methoxy The
excess
groups
and
the
in the MO-N
the
geometry
and
distance
two
and
N-N
anion may
[M004]~-
suggests linear
and NEt3
formula
showed
overall
phenylhydrazine
to have
be viewed units
no MO-MO
nature linkages.
of
the as
acting
bonding.
the MO-N-N The
two
electron
as The
unit
49
Ph \
N
N
/Ph
I’
/ N
(27)
N
PhlN Ph
Bond
distances
are
.Mo3
=
3.465
MO-N
=
1_823(9)(av)
Mol..
count and
is
consistent
therefore
oxidation
the
state
various
Thus,
with
of
products MeOH
in
of
the bond
former
was
distance
W(NPh>C14
ligands
coordinated
with ox+ygen donor
1,227(12)g(av)
acting
as
molybdenum
three
atoms
electron
are
donors
formally
in
shown
reacts
2,3-dimethyl-2,3-butanediol
to
of
various the
alcohols
steric
be
the
as
in of
(28). a
presence (pinacol-H2,
The
triple of
dimeric
Cl ] 2 22 W-N-Ph
bond
the
presence
of
the
of
with to
give
base
alkoxides.
species
were
formed,
group
is
The
linear
structure and
the
C621,
N('Bu)~ L-H21
in
requirements
the
@Bu)NH2
[W(NPh)(p-OMe)(OMe)
suggestive in
with upon
presence and
is
Zigands
W(NPh>C14
depending the
[W(NPh>(u-OMe)(OMe>312
W-N
diazenido
=
[61]_
interaction
gave
the
octahedrally
(0)
2.1.5 CompZexes
The
with
N-N
two
moles
three
of
products,
WL3,
50
OMe
OMe
Me0
OMe
,N
Ph
tie OMe
Bond
distances
are
w I.. w 'W(u-O)(~?rans
NPh) w-o
W2(NHPh)L5 WL3.
The
that
of
and
OMe
= 3.467(4) =
W(u-0)(&s
2.16(2)
crystal
structures is
=
l-61(4)
NPh)
=
2.05(2)
= 1.90(2)Z(av)
whilst
W2(NPh)20L2(L-H)2,
W2(NHPh)L5
W-N
shown
of
the
in
(a)_
a
latter
larger two
amount
compounds
of were
I-0
“Q/O-\ O'bN-" 0
Bond
distances
Ph
/
are
W-N
=
2.02(21
w-0
=
1.80(2)-2.00<2)'A
pinacol
gave
determined
only and
51 The
W-N
distance
the
protons
of
determination The
is not the
consistent
proposed
they
were
compound
with
NHPh
a triply
ligands
observed
were
in solution has
W2(NPh)20L2(L-H>2
not
NPh
resolved
'H NMR
by
the
bonded
group in the
and
structure
spectroscopy
structure
shown
in
although
C631_
‘;
n
“-O\/O “\ /O> o-w-
N
O-?“\OCm)
“\ Ou”-Ph
Bond
distances
are
W-N
= l-75(5)
w-u0
N)
= 2.30(3)
w-o
w-o(tmns
The
W-N
distance
is very
oxygen
tansto
be
protonated
the
Self theory
levels
systems
the
S-S
Reaction resulted mole
the
are
lowest
levels
and of
equivalents I
551
for
very
a triply
long
W-O
bonded
bond
NPh
distance
ligand.
The
is assumed
to
and suZphur donor complexes
have
with
been
earlier
of
found are
the
isomeric of
performed using the local density 22the anions, For cMoS41
[Mo3Sg]
MO-S
high
absorption
bonding,
and
the
of
(Me3Si)2S,
was
isolated
The
(or:g_7:1)
cage
and
partial
a compound which
X-ray
bands.
the
weakly
MO d-orbitals, mixture
but
calculations,
to be Mo(V1)
non-bonding
an
in cleavage
(NBu~)~CMO~S~ _4502
the
[MoS4] 2- and
re-assignment
molybdenums
antibonding
eight
for
are in accord
require
terminal
with
typical
= l-82(4)-2_00(5)g
[631.
calculations
method
calculations
and
thiatungstates
consistent
(LDT)
group
oxygen
ThCnnoZybdates,
2.7.6
MeCN
the NPh
short
= 1.89(4)
of
central bonding LDMO
the
energies
For one S-S,
cMo3Sgl Mo(IV).
of 2-
the
, the
In both
weakly
is MO-Sx * [64]_ 4with (Me3Si12S
[MogOa61 reduction
with
of Mo(VI)_
empirical
formula
crystallography
showed
With
to
in
52
consist only
of in
almost
the
equal
identity
amounts
of
one
of
CMo3S8021
terminal
'-
ligand.
and
The
[Mo3S70312-
which
structures
are
r
differ
shown
in
I 2-
O\\
/\
/\
s,qMo2,
//o’s
,M*‘\
/Ho3
~
<311
Bond
distances
are
Mol-Mo2 Mo2=0 Mo2-S(S2) s-s
The
central
(VI),
The led
atom
95Mo
to
and
is
=
2.896(l)
Mol-Mo3
=
3.047(l)
=
1.677(S)
Mo3=0,s
=
2.395(3)
I
2.051(4)%
oxidation
l7 0 NMR
reactions
of
dinuclear
The
in
The a
in
MeCN.
dark
This
one-electron
MoBr4
is
the
that
of
a
of
of
to
outer
ones
MORBID
X-ray
two
from has
state
SMe2
and
the
COAX
gave
complexes
solution
the
ligands-
and thf
4gave
interaction
of
was
iron
a
almost
compound
cubane
which
Electrochemical
reversible anions
[68],
a dark
brown
Mo2C02S4(Rt2dtc)2(CO)2(MeCN)2
distorted
[MS4]2-
(NEt4)2[MoS41
series
pattern
and
2-
the
of
extensive
MoS4
in
by
solution
powder
the and
[673_
prepared a
oxidation
corresponding
MeCN
the
with
measured
corresponding
chelating
one-electron
complexes been
with
Its
the
in
iron
was
MeCN
in
Mo2S4(Et2dtc)2
showed
in
type-
give
oxidation
have in
derivative
by
2,898(6)
and
of
characterized
surrounded
Recrystallization crystallography
this
fully
reversible
reduction
a number
delocalization
cobalt
or
c661.
(NEt3H)SPh
first
iron
2_287(3)-2.458(2)
and
(NEt4)3[Co(MoS4)21
and
the
1.646(14)
=
C651.
[Fe3S2(WS4)3]4-)
electron
of
the
=
MO-uS
(PPh4)2[S2MoS2MoBr3(SMe2)1
compound
CoCL2
Interaction
X-ray
of
of
revealed
product.
with
spectra
compounds to
tetrahedral
studies
Raman
green
heterometallic
has
reported
respectively
terms
solution
identical
and
also
CFe(B20)2(WS4)212-,
discussed
of
(IV)
were
(PPh4j2fMoS4j
complexes
resonance
(e-g_
state
studies
(PPh4>2cS2MoS2Mo(NO>2Br21
ions
S
S
S
structure
which
53
co \
\
co co
I/ -S
/I
S
co
S
/
s-
S
MO
( ‘I
4
-MO
S
-S
‘I
(32)
PieCN
S
Bond
distances
are
MO-MO
MO-pS(Mo)
original
lengths bond
are
length
very
unit
similar
of
the green
Similar but
reaction
reaction
structure
seven
with
of
2-
the
useful
complexes route
to
+tInds
starting
the MO-MO
and MO-lJS
material.
The
the MO-uS(Co)
(33) type
-
W
VI
molecule
with
tmds
gives
linkage
original
bond Mo=S
C69I. (tmds)
causes
a
S(S2)(S2CNR2)2
structure
whose
gives
reduction
MoS(S~)(S~CNR~)~
is shown
to MO(V)
which
(see
Ls known
in <33). later),
to have
a
c701. Mo(L-L)2(deazjn
diethyldiazenedicarboxylate) These
and
tetraalkylthiuramdisulphides
coordinate
[MoS4] . CMo02S21Lto
similar
Compounds
= Z-316(1)
reaction
of
with
in the
it becomes
cwVIs412-
to give
MO-vS(Co)
is recognisable
to those as
CWS41L-
redox
= 2.680(l)
= 2.533(1)X
is increased
based
MO-CO
2.788(l)
Mo2S4(dtc)2
Reaction ligand
=
= 2.360(l)(av)
CO-CO
The
MeCN
readily react 18 0 complexes
are
(L-L
readily
prepared
stoichiometrically 180Mo(L-L)
2
and
= dtc, from with
dtp;
deaz
Mo(CO)~
and
180 Mo(L - L) 2 1711,
2
= and
deaz-
so provide
a
54
s
s\
0/
s\u
CNR2
S’
(33)
I
Bond
distances
are
w=s = 2.136(l) w-se21
Anilinium-g-octamolybdate of aniline
crystals
were
presence
of
EtOH
gave
slowly
a purple
which
moities
with
to the
three
environment.
2 units
the
hydrogen
alternating crown
bonding
the anion,
EPR
spectra
proton
transfer
It is suggested
photochamical 17 0 and
reduction 183 W NMR
Na10 [H 2 W 12 0 42 l.27H20 change with pH and
that
confirmed
The
the
phenylhydrazine
of
and
NEt3
(NBu4)2[Mo8020(NNPh)6]
a crown
of
six oxo-bridged
MO
three
types
resemblance
reported)
to that
by replacement
c731.
of WV
irradiated
localized
of molybdenum the
precursor
of
three
(NH3Me>8~Mo8026(Mo04>23‘2H20
MovO
the
of
cation BCMO~O~~(MOO~)~I
(OH) sites resulting from a 5 to a bridging oxygen atom in undergoes
a four-electron
[74]. spectra
and are
the (pH 2.5).
and cis-[Mo(NNPh)212+ [Mo04122CM0041 units acting as trtdentates
giving
from
which
excess
units
two distinct
through
in water
[72].
showed
a close
is also
isolated
of Moo3
crystals
two more thus
bears
structure
of
which
by
centres,
by c
crystal
with
oxomolybdate
capped
structure
formation
anion
crystallography
Mo(NNPhj2 The
Single show
the
from
been
crystallography
@-[Mo~O~~]~-
solution
are
has
solution
a-(NBu4)4[Mog0261
X-ray
(whose
EMo~O~~I~&S-MOO
an aqueous by X-ray
known
between
separated.
centres
dihydrate
with
characterized
the well
Reaction
= 2.454(l)-2.528(2)
po tyanions
Homonuchar
interaction
W_S(dtc)
= 2_208(2)5(
s-s 2.1.7
= 2.588(l)
W-S(ax> 2-403(Z)
= 2.366(3),
have
been
Na6[W70241_14H20.
fully
consistent
obtained The with
for
acidified
spectra
the known
of
solutions
[W702,+16-
solid
state
of
do not structure.
in
'Paratungstate to those
2.1.8.
of
formed during condensation of [WO,]*- has spectra identical 6as previously thought [75]. [W7024] , so it is not a hexatungstate A'
HeteronucZear
A 31 P NMR
poZyanions
study
has
H*/[MoO~]~-/[HPO~]*-
system.
pentamolybdodiphosphate their
degree The
dynamic
anions
tridentate
ring
bonds
whilst
involves anions
or
two
of
example
a g-type
of
atoms
in the
a single
exists
whose
by a common
groups
on
members
processes,
temperature
MO-O
ring
side
the and
low
of
differ
capped
the
only
by
one
features
of relatively
although
processes
The
by
ring_
temperature
making
process,
Similar
bonds.
Mo6018
either
the breaking
of
octahedra
which
6 the
and
isolated general
not
occur
long
fully for
MO-O
defined,
the
other
linked
family
groups
by
of
sharing
is completed
revealed
three
by X-ray
the
corners.
first
The
W06
octahedra
and
One
As
central
to three
by a hydroxy
CaC
compound
of polyanions-
is linked
heteropolyblue determined
in the
determination
the other
sphere
structure
isolated
is the
outer
group
oxygen
[78]_
5[H6M~12040]_18H20 * diffraction_ It has
as the 8-[SiW 1 14- anion C791. l4 12 40 anion [NaP5W3C01101 - is formed as a by-product in the 6and has been characterized by X-ray crystallography.
one
has
been
the
same
structure
The
cp2W180621 approximately
the Na+ plane Line
encapsulated appears
its
sharing
while
reduced
been
the As III/W
edge
are
heteropolyanion
has
structure
for
two
its coordination
and
anion
A crystal
A four-electron
four
equilibria
Mo/P<2.5
complexes
dynamic
structure
is composed
two wo
the
the
[76]_ 4the a-[Mo80z6] , [(PhAs)Mo 0 14- and 17 ' 25 0 NMR spectroscopy_ been investigated using
8-tungsto-Z-arsenate
of
structure
with
and
related
strong
on
the pH varies
higher
K7~AsW8030As(OH)~_12H20_
atom
of
involving
second
cleavage
pH>5.5
[PhAs0312-
inversion the
have
out
C771.
A new
of
of
anions
- shows
c(PhAs)M0~0~~1
as
structurally
CMO~~I~-
Mo6018
series
behaviour
are
carried At
of protonation
[(PhAs)2M0602414three
been
D5h ion
symmetry located
containing (2:Z:l:l) and
the
anion
five
lg3 W NMR
does
not
to be necessary
interesting
and
and
consists
within
some
phosphorus spectrum
exchange
for
of
a cyclic
the polyanion
the
in solution.
formation
with of
array
the This
atoms.
readily
vanadium
on
the
substitution
anion, products
and
but
gives
sodium
Na+
PW6022
axis,
asymmetry
of
It has
five
fivefold
The
free
of
synthesis
ion
units above
rise
to a
is tightly
its presence
Reduced were
forms also
of
this
described
C801What
is thought
K28Li5CH7P8W480184 crystallography.
to be
1_92H20,
the
largest
has
been
It crystallizes
known
prepared
spontaneously
phosphotungstate, and
characterized
from
LiOAcjHOAc
by X-ray buffer
solutions
56 [H P W 0 1 which is Of K12 2 2 12 48 degradation in the presence
itself of
obtained
amine
from
according
by
[P2W1806216to
the
scheme
alkali
(34).
CQ2-P2W170611
t
lo-\ lo-
cal-p2w170611
(34)
The
structure
linkage
of
of&_four by
EP2W180621 four from
the
The
in "
in
solution
species
V
the NMR
to
the
tungstate " 0
being
in
P:V:W
a
are
in
the
form
derived
adjacent
of
a
from
W06
crown
the
formed
well
octahedra,
by
known
two
from
the
structure the
cap
of
and
cSl1. series
ratios
of
of
dependent
solutions
l:6:6, The
spectroscopies.
2-
+
was
upon
of
1:8:4
sodium
and
compositions pH,
but
1:10:12 of
no
phosphate, have
the
vanadate
been
and
studied
by
vanadophosphotungstates
solution
ever
contains
just
one
NMR
spectra
confirmed
the by
of
species
of
the
structure
surface
yellow
from of
The
[W041 two A
to
-
heteropolymolybdate 2-
and
cp2TiC12
compounds
based
on
are
that
changes
and
charge
+
2[cpTi(Mo5018>1
and in
very
crystallographic
resultant
activation
3-
+ H20
the
simple_
cpTi.
reaction
2cp2TiC12
prepared
Mo=O
unit
the
formation
particularly
terms
six
polyhedra
dichloromethane
5CMo2071
and
of
loss
is each
[821.
In
led
the
formed
tungstate 31 P and each
P2W1204g
subunits
belt
ions
33-
[H7P8W4801841
the
acidified
similar,
study of
CMo60191
in
the
on 2-
bond
delocalization
2C5H6
CH2C12.
The
the
NMR
molybdenum
with
were
these
IR spectra
compound
replacement
lengths in
4Cl
corresponding
with
the
+
of
and
in
similar
[831_
Reaction
of
Na2[W041
and
ZrOCl2
followed
by
addition
of
NMe4C1
gave 183
Various
(NMe4)2[H2ZrW50191spectroscopies [W601s1'-
one
discussed
were
all
physical
consistent
measurements with
a
including
structure
IR,
analogous
UV
to
and
that
W
of
[841.
Addition
of. (Me3Sij2S
to
(NBU~)~CM~W~O~~I
(Mq
= Nb,Ta)
in
dry
MeCN
gave
NMR
57 (NBU~)~CM*W~CI~~SI complexes The
is replaced
I7 0 NMR
spectrum
in solution
terminal
was
fully
to be isolated
was for
_ A crystal
the heteropolytungstate but
atoms,
structure.
an ONb 2 oxygen
and
oxygen
II) or
(isomer
shows
isomer
solution
2.1.9
two ONbW
OW2
retention
the
metal
are
were
possible
(isomer
oxygene
I>,
other
structure
0
[851_ (M' on
= Mn,Re)
the Mn
contiguous
disordered
with
d
M'(C0)3
to
compound
bridging
in the
solid
coordinated
to
two ONbW oxygens and one OW2 ;17 III>. 0 NMR spectroscopy
(isomer
both
three
same
first
determination
to Mn by
original
cryetallography.
fac-[M'(CO>3(MeCN)31Cl
in the cluster
but
of
is the
transition
structure
oxygen6
three
in the
by X-ray
This
an early
dietereoisomers
II to predominate,
isomers
are
also
present
in
C861.
Complexes
The
with nitrogen
unusual
MoC14(MeCN)2
complex
with
interaction
showed
with
observed.
with
metals
at Nb or Ta
confirmed
coordinated
the heavy Three
wae
consistent
resonance
1 reacts
state
oxygen
This
sulphur.
(NBu4)4tcis-Nb2W4049_
oxygen
shown
the
C(CO>3M'[Nb2W40191
showed
the
by
as no M'=O
polyoxothioanion
give
in which
and
of MoC13(terpy) a seven
(35) with
phosphorus
donor
MoN(C1>(N3)2(terpy)
Me3SiNj
it to have in
and
subsequent with
and
formed
addition
Me3SIN3.
coordinate
the nitrido
was
of
either
terpy
A crystal
pentagonal chloro
2 igands
axial
or alternatively
structure
bipyramidal
ligands
by reacting by
determination
stereochemistry
as
1871.
N-N-N
N-
Bond
distances
MO-N(N$ MO-Ncterpy)
strong
bans
N
are
Mo-N(nitride)
The
N-
effect
= l-662(7) = 2.076(7),
MO-Cl
= 2_719(2)
2.114(6)
= 2_235(5)-2.285(6)x
of
the
triply
bonded
nitride
causes
the
long
MO-CL
bond
58 distance. Various
mixture 13 C NMR
pinacols
of
reacted
with
(pinacol)W(NR2>2(NH2R)
studtes.
although
were
not
However,
the
in
isomer
same
(RN)2W(HNR)2
and
the
solid
for
each
(R
= 'Bu)
(pinacol)W(NR)(NHR)2 state
each
pinacol
shown
in
a
give
by 'H and
as shown
pinacol
as
to
gave
only
one
(36)
and
(37)_
isomer,
NR
RNH2 I
II
RHN\W cF3
o
RHN’
cF3
CF3
I 0
cF3
2
CF3 CF3
(37)
(36) R
Bond
distances
tBU
=
are
(36)
The
tungsten
(38)
imino
considered
to
used
been
W=NR
1.742(3)
1.753(4)
W-N
2.201(4)
1.927(4)x
atom
the
in
each
groups
are
be
for
ammoxidation reactions
investigated by
PhC(O>NHNH2
of
and X-ray
provides
together
short,
atoms
were
quite
showing
trigonal
for to
structures
first
of
located)
significant
(X two
of
as
CBS]. with double
bond
in
0,s)
the
and
bond
(38).
distances
character
are
catalysts
PhC(X)NHNH2
products
hydrazido
diazenido
in
molecules
heterogeneous
of
group and
have
been
'end-on'
It
for
group the
NHNHR
a N2C(0)Ph (for two
distances
electron
and
bonded
contains
(I-)
bond
have
Mo02(PhC(S)NMe0)2
characterized
shown
The the
These
[881. =
interaction
NHNHC(O)Ph
stereochemistry,
(37).
molybdenum
structurally
the
in
acrylonitrile
The
molybdenum with
different
the
Mo02(PhC(X)NMe0)2
the
for
bipyramidal
axial
but
models propylene
the
group
are
a
crystallography.
diazenido(2-) hydrogen
has
equatorial,
between
hydrazido(l-)
moities
case
homogeneous
The
determined
(37)
which
the
hydrazido being
delocalization.
quite
59
Ph
0 *
c’
/ Ph
N4
\
S
C-
/
/
N3 I -
/
MO
7 -
y5Ii
Ph
N6 ‘C
s
1
I MeANY \ Ph
Bond
distances
are
MO-N3
=
1.758(5)
N3-N4
= l-292(4)
#o-N5
= 1.938(4)
N5-N6
= 1.361(7)
MO-O
Reaction
= 2_106(av)
between
MO-S
Mo02(PhC(S)NMe0)2
Mo(NHNC(S)Ph)(N2C(S>Ph)(PhC(S)NMeO) structure
shown
The give
in
complexes
showed
molecule
is rigid
signals
spectrum
red
[MC1(NNMe2>2(PPh3)21Cl
it to have
and the
in solution
purple
indicated
confirmed
porphyrin
other.
was
shown
gave
to have
the octahedral
react
a structural
pentagonal as
shown
with
PhP(CH2CH2SHj2
determination
on
in MeOH
to
the molybdenum
bipyramidal
structure <40). The 1 31 two non-equivalent P and H NMR
by
1901.
The
study
which
PhC(S>NHNH2
c891,
M(NNMe2)tPhP(CH2CH2S)2}2
compound
the
and
e 2.445R(av)
They
and,
2,086
2.0928
1.909(15IZ(av)
The
atom
the trans
nitrogens
for are
tungsten the
distances
of
2,298
the others.
normal
[913.
has
been
porphyrin
as a result,
eclipse
W-N
W(TPP)(0)(02)
an unsymmetrical
this.
different and
complex
0x0
of
to one
peroxo the
and
2-87851 f or
The
W=O
and
and
coordination
is 1.492 and
isolated
groups
porphyrin the
W-0(02)
and
side
its 'H NMR a structural
of
the
are &a and
eclipsed distances
this
N4
leads
nitrogens of
plane
of
to each to very and
l-752(13)
and
Ph
\
c
-N
\
s,i->s\ I
,/i”\N_.i”-ph
Me
- /‘c
S
/
N
<=I
I Ph
Bond
distances
are
Mo-N(NN)
MO-N(NHN)
= l-789(4)
MO-O
=
= l-972(3)
MO-S
2.051(3)
= 2.436(l)-2.504(1)x
Me2 I N I
Bond
distances
are
MO-N MO-S(PX) MO-P
= l-775(6) = 2.499(3) = 2_517(2)~(av)
N-N MO-S(eq)
= l-265(9) = 2.498(3)-2,548(2)
61 Oxidation CRC13
gave
WO2Br2L
cw*05L21*+ observed
of LW(CO)3
which
whose
made
this
by
with
slowly
direct
of
with
cont.
acid
to
of L'Mo(C0)3
Somewhat
first
yielded *+
with
excess
bromine
it transforms different
in
to
chemistry
is
L' = N,N1,N'm-trimethyl-l,4,7-
gave
CW205L’23
with
In solution
c921.
(where
bromine
nitric
hydrolyses
oxidation
bridge
L'M(C0)3
Oxidation
oxidation
fs unknown.
a monoxo
oxidation
triazacyclononane),
tungsten
structure
contains
in the
further
(L = 1,4,7-triatacyclononane)
[L'M(C0)3Br]Br
[L'M02Brl+. 193,941
more
on
In the
case of 2+ was ~Mo~O~L'~~
while
dilute
which
HN03
[951.
The
crystal
?*
structure
of
1~1LT was determined
CMo205L
and
is shown
in (41)_
2+
\/\ L distances
The
compound
In the
Mop0
= l-695(7)
PO>
= 2.290(9)
Reaction colourless
unambiguousLy
be reduced of
1.73BM
reductiona
tungsten
one-electron
of
can
moment
one-electron
0
(41)
A
0
are
MO-N(tma
magnetic
N
MO -
N
N-
Bond
o-
MO -
.N -
system
chemically per
are
both
reductions
= 1.898(l)
.s-
0) = Z-325(8),
to the deep
molecule.
seen
blue
2-355(8)A
+1 cation
ElectrochemFcally,
two
which
has
a
reversible
[951
cL'W02Xl+
and
[L'2W205]2+
show
single
reversible
[94].
of WC14(PMe3)4 WH6(PMe3j3.
MO-u0 MO-N(trans
The
as the molecule
with
LiA1H4
structure
in ether in solution
is fluxional
and
at -78OC could
crystals
led not
to the
fsolation
be determined
suitable
for X-ray
62 diffraction
could
not
be obtained.
NH2($J1-C2CH)()J2 -02CH)(PMe3j3 wide
temperature
bidentate
range.
format0
whose
The
groups
spectra
and
AND
also
2.2
MOLYBDENUM(V)
2.2.1
Halides and halo complexes Chlorination
the
product due
to MO-Ft
chain
structure
temperature consistent
at
with
Interaction monomeric
MoCl
structure
(42)
4
sealed
in the cooler 720 and
exchange
680cm
tube
region -1
of
per molybdenum
and
decreases
exchange and
in a polymeric
and
X-ray
’
The
and
crystal
shown
in
The
and
with chain
and
E961.
MoF3C12
with
IR spectrum showed -1 _ A polymeric
446cm
moment
temperature. structure
in CC14
diffraction
showed
at room
This
is
[97].
suspension
Ft to have
gave the
C -Cl
1
'N'
(42)
are
MO-N
= 2.079(4)
N)
= 2.266(l)
in dichloromethane
MO-Cl(c&
reacts
(PMePh,)2[Cl,Mo(p-S2>2MoC141_2CH2C12_ MoBr4
a
E981.
MO-Cl(i%ans
from
gave
The magnetic
diisopropylcarbodiimide
(ZPrNC(Cl>NZPr>
Cl
Mo(S2)C13
tube-
at 494
b suggested.
MO
distances
over
monodentate
exchange
120-150°C
the
and MO-F
cl\I/N\
Bond
at
was
of MoC15
studied
between
site
bridging
magnetic
.
in a long
fluoro
is 1.29BM with
indicated
phosphinelhydride
were
TUNGSTEN(V)
of MoF3
condensing
bands
Reaction with CO2 gave 1 31 H and P NMR spectra
S7NH
and
structures
(43). The
The
subsequent of both
MO-MO
addition
were
distance
with
3 corresponding of
determined,
suggests
(PMePh
N)
>Cl
they
to give bromo
(PMePh3)Br
a single
= 2.343(l)%
are very bond
complex
in CH2Br2
[993.
similar
was
made
solution. and
are
63
S
Cl
cl\\ //q
/p
Cl
2(43)
clq”\qM\ Cl
Bond
distances
Cl Cl
:
are
2-
2-
[Mo2(S2)2C181
MO-MO
2.875(l)
2.855(4)
MO-S
2.422(1)-2.429(Z)
2.412(6)-2.424(6)
MO-X
2.407(l)-2.518(1)
Z-566(4)-Z-688(3)
s-s
1.981(l)
1.969(9)x
Trimethylsilyldialkylamines, (1:l)
MoOC14
in
aprotic
complex 2:l
solvents
MoOC14
but
such
excess
+
Interaction crystals
of
salts
in
+ 2
Me3SiNR
causes
3Me3SiNR
+z
of of
PPh4Cl the
or anion
moisture.
X-ray
crystallography
structure
<44)_
The
structure
product
the
reaction
the
is
to
with
of may
the be
compound
regarded
ClOO,lOll.
At
is
occur
+
to
give
2 Me3SiCl
Mo(IV)
+ Me3SiC1
+
with with either
the R as
oxygen
=+-tolyl a grossly
ClOll.
(Me3Si)20
(Me2S)C13W(SR>2WC13(SMe2)
[C120W(SR)2WOC12]-
with
tetraethylhydrazine
(MoOC13)2tds
MoC~~(NR~)(NHR~)~
AsPh4C1
react
compound
+ Me3SiCl
MoOC12((NR2)(NHR2)
transfer
+2E!
Et2,pip,pyroll) a MO(V)
gives
the
+H -
2
=
give
MoOC13(NHR2)
Me3SiNEt2
CS2
oxygen
2
to
2
CC14,
CR2
ether
dichloromethane
Me3SiNR2
MoOC14
as
while
in
or
+ Me3SiNR
MoOC13(N2Et4)
proportions
Me3SiNR2,
dichloromethane
MoOC14
In
[Mo2(S2)2Br81
gave coming confirmed distorted
from the
r
Cl
/
0
Bond
distances
W-W
confacial
2.878(Z)
w-s
=
2.427(3),
W-uC1
=
2_604(7)g
bioctahedral
or
as
filling
crystal
two
the
structure
Oxidative
of
Interaction
is
this set
up
addition of
the
formed by
of
latter
square
pyramids
octahedral the
(pyH>2[Mo203C14(OEt)(HOC6H4C02)]
MeCN
0
= 2.378(9)
=
interactions The
p-to1
are
w-cl
W-Cl
’
H2
at
with
known
60°C
to
TlCBF.1
and
WC12(PMe3)&
is
as
gave
~lcl~
gave
MeCN
the
In
edge
ti
crystal described
analysis.
structure as Bond
of
+e --f
in
(45)
[WH2C1(PMe3)4]+ square
[103].
and
in
scheme
reaction
(461
+
CwH2C12P43
tS MeCN
MeCN
CWH~C~~(PM~~>~~(BF~)
dodecahedral distances
long
WH2C12(PMe3)4_
(46)
EWH~CIP~(MGN)
be
two
oxidation-
WH2c12p4
The
with
complex
determined
or
an
[102].
salicylate
been
~~2C1(PMe3)4(MeCN~~+.
electrochemical
sharing
positions
has
2.450(3)
are
but
the
W-Cl
=
with
U-N-O
was
hydride 2.438(6)
12+
determined
ligands
were
and
=
W-P
and not
the
cation
detected
may
in
the
2-482(6)-2.595(5)x
c1041. Tridentate
Schiff
Prepare
MO(V)
MoOCL2L
with
magnetic
ligands
gave
dinuclear
have
severely
complexes_
depressed
bases The
O-N-0
moments complexes magnetic
of
and
donor
N-N-0
ligands
approximately Mo203C12L2 moments
donor (L)
gave
1.7BM.
The
thought ElO51.
sets
to
be
have
been
monomeric N-N-O 0x0
used
to
species donor
bridged
set and
which
0
Et
0
A\ II ‘I
1/
CI
2-
/
MO
Mb
I’
(45)
\ Cl
O\y/
0
/b
OH
I
Bond
distances
are
MO-MO
= 2.646(2)
Ma=0
MO-JIO = 1.912(av) Mo-O(sal)
A serles Schiff
base8
prepared
of
various
by reacting
to be dimeric
with
Mo-VOEt
= 2_306(14)(av)
of complexes from
the
alkoxide
= 1.964(10)
MO-Cl
type
substituted
(N)14)2[MoOC153 the
= 1.670(14)
MoOClL
= 2.399(S)-2.432(6)%
(L = tridentate
salicylaldehydes and H2L
oxygens
and
in EtOH.
acting
0-N-O
The complexes
as bridge8
donor
ethanolamine) are
as well
were thought
as chelating
11061_
2.2.2
I&nomeric
The organic monomeric to give compounds changes of
visible solvents
0x0
compZexe8
absorption have
been
in dichloromethane CM~O(TPP)(~IIISO~X
in the absorption disappear8
of MoO(TPP)X
solution.
in CH2C12/dmso
are photosensitive
MoO(TPP)X
spectra
investigated_
when spectra
a8
the
EPR
The The
axial
mixtures
irradiated suggeet silent
compounds
compounds
shown
is substituted
c1071.
In 2-Methf
reduction
region
to MoO(TPP). is generated
in
to be
ligand
in the Soret
MoO(TPP)
(X = F,Cl,Br,NCS)
were
by dmso
MoO(TPP)X and
the
The
EPR
ClO81.
signal
2.2.3
p-0x0,
The
p-sulphido
kinetics in
[Fe(phen)313+ the
rate
the
first
With
the
of
x
aquo
The
have
the
compounds of
solvent.
On
ligand
The
with
Mo(V1) of
it
complex
of
give
the
be
Mo(IV)
this
Solution8
but of
an
is
in
solution
equilibrium
the
MOOR
in
converted
to
(~~H>~~Mo~o~(Ncs)~~ with
water
the
the
with
L-L
with
0.5
yielded
it
was
does
not
obey
Mo(N-p-tolyl)(dtc)2
given
trapped
by
the
its
Beers
Law
The and
with
further
compound
is
PPh3
which
reactive
and
it
mixed
(0x)~(H20)~)
Mo(V)/Mo(IV)
with a
were
obtained
electrons
which
the
oxidation
mixed
presence A
of series
(c-hexyl)2)
were
oxygen of have
(monooxo
bridged),
bridged)
and
The
by
oxygen
catalytic
to
not
adduct.
reform
cycle
they
by
dimers rapidly
MO(V)
species
been
prepared.
M0204(R2C02)~
of
pulse decay
They
the
the
(t
MO(V)
carboxylates are
(dioxo
of
the
bridged),
(monooxo,monosulphido
(dmmp>OMo(p-O)(u-S>Moo(MeOH)
4,6-dimethylpyrimidine-2-thione)
has
been
(L
for
=
MO(V)
radiolysis. Slowly
reform with
2-
[Mo204Ln1
reduction
generated state
Mo203S(R2CO2)2
complex
complexes
is
gave
could
dimethylacetylenedicarboxylate
react completing
PPh30.
+ MoO(N-p-tolyl)(dtc)2
reaction This
as
Mo(N-p-tolyl)(dtc)2 thus
reacts and
the
oxidation
of
[1121. The
_
dissociation
Mo(N-p-tolyl)(dtc)2.
MoO(N-p-tolyl)(dtc)2, PPh3
by
of
cis-MoO(N-p-tolyl)(S2CNEt2)2
x
scheme
complex
isolated,
of
reaction
with -l/l 13M
is
prepared
were
=
clO91_
solution
compounds
k
constant
were a
species,
oxidation
[Mo(N-p-tolyl)(S2CNEt2)2120
dimer
undergoes
[Mo(N-p-tolyl>(dtc>2120
the
on
rate
that
process.
constant The
systems
indicates
a hydroxy
investigated
and
reaction
which
overall
the
rate
the
phen)
HF
these
Similarly,
to
PPh3
spectrum
for
bipy, 40%
water
and
both
for
order
also
In and
[1111.
that
Support
= in
25OC_
mechanism.
were
and
oxidant
involves
second
sphere 4+
(L-L
at
and
determining
sphere
outer
[Mo3041
dissolved
[1101.
oxo-imido
electronic
be
inner
[Fe(H20)613+
examined
a
Mo203(L-L)2(NCS)4,
equivalent
proposed
rate
with
an
by
reductant
pathway
and
digestion
Mo~O~(L-L)~F~ gave
is
Mo~O~(L-L)~F~
the
been
in
react8
to '+
[M02041~+
predominant
by
expected
[Mo202S21
order step
which
Mo204(L-L)2(NCS)2
mole
solution
transfer
is of
interaction
EtOH
of
first
complex,
CFe(phen)313+
in
is
oxidation
, probably
Oxidations
known
aqueous
[Fe(OH>1'+, -3M-1s-1
10
same
the
reaction
electron
probably l-3
of
comptexes
prepared
edta,(L-cystJ2,
dimers In 1
with
the 5
l/2 dimers
hydrated
absence
-10s)
of
but
in
cl131.
R2CO2-
CR2
general
=
Me,c-hexyl
formulae
bridged) (dmmpH the
and
Mo203(R2C02)4
Mo~O~S~(R~CO~)~
by
oxygen the
(disulphido
El141_ = interaction
of
6'7 Mo02(aca+
with
determination
excess
atom
octahedral
Bond
distances
and
MO(V)
= 2.180(7),
2.209(7)
distance
compounds
with
one
molybdenum
l-667(6)
=
t l-911(5),
l-933(5)
suggestive
bond of
of
lengths
this
type
with shows
it
known
type
a
single
refer of
to
bond
the
structure
the
extra
is
possible
the
been
with
simple
is
molybdenum
discussed
interacting form
compound
coordinate
have
ligand to
and
five
in
terms
both
metal
of
dimeric
adducts
cll51. of
have
the
been
prepared
reductions of
coordinate
tungsten
Dissolving subsequent
determination
the
the
They
are
atoms
addition
of
P2S5
thought
and
to
they
cyclic
CR2
= Me,Et,bz; show
the
two
(1161.
gave
structure
= pyrr,pip,
reversible
voltammetry
= morph,pip)
have
R2
the (48)
corresponding with
five
C1171. in
of a
(R
CMoS412-
timescale with
(NH4)2cMoS41
revealed
Mo~(S~>(~-S>~O~
on
Mo2Sq(R2dtc)2
from
W202S2(R2dtc)2
compounds.
in
is
shorter
W2S4(dtc12
sulphur
structure
(47)
= 2.535(6>2
examples
one-electron
and
crystal
2.320(3)
structure
Interaction
in
Mo=O
MO-N
Compounds 4-Memorph)
A
shown
MO-~0
coordination'
This
MeOH_
coordinate.
2.489(2)
The
'crevice
five
= 2.435(3),
Previous
atoms.
other
MO-S
bond
diamagnetic.
of
refluxing
= 2.660(l) =
Mo-MeOH
atom.
in
stereochemistry
are
MO-uS
MO-MO
the the
MO-MO
The
dmrnpH
revealed
dilute
(N3uq)Br
HCl
gave
stereochemistry
and
Mo~(S~)(~-S)~S~
apical
positions
solution
shown
a dark
(NBu~)~[Mo~S~OI, very
structures
as
gave
A
crystal
the
known
similar
to
with
disorder
in (49).
red
between
solution structure
oxygen
and
68
s\,ASlw \
S
/
I
/
c-
s
IS
/
(48)
\
S
\
\
s-c
S
\
/
RN
NR
2-
S
S
Bond
distances
are
Mo=O,S
MO-MO
= 2.811(l)
MO-W
= 2.307(3)-2.320(4)
= l-945(6),
MO-S,
l-986(6)
2.376(4)-2.398(4)x
= L
The
MO-MO
suggests, dimcr
distance
is
but
not
rather
does than
a
indicative
of
a
unequivocally
solid
state
single
bond.
prove,
mixture
of
the
evidence
Spectroscopic
existence
[Mo~S~O~]~-
unsymmetric 2anions [Mo2Sg]
of and
the
Cll83. Interactlon Spectroscopic the
to
complex those
compounds
are
this
unit,
core
EMS4]'-
evidence
tungsten
similar
of
of
useful for
with
S
suggested was
in
that
determined
other
M(V)
precursors example
dimers for
M2Sq(dtc)2
hot
thf
they and
is
yielded
have shown
containing the
preparation [1191-
the
similar in the
[M2S121
structures
(50).
The
syn-M2S2 of
2-
other
anions. and
that is
structure unit. species
of
These containing
69
2-
s
w\ \ I
w
/
s-s
I
\
s-
sLS
SAS
Bond
distances
are
w-w =
The
reaction
2.836(2)
w=s
= 2.116(5)
w-Ils = 2.320(6)
w-s
= 2.387x(av)
between '-
CMo202S2(SCH2CH2S)21 also
isolated.
they
are
The
very
phenylhydrazine
anion
crystal
similar
to
and
the
structures each
other
0,s
‘s\
“zC
II/\I1
and
MoO(SCH~CH~S)~
analogous of and
salts shown
distances
gave
of in
both (51)
anions
the anion
CMO~S~(SCH~CH~S)~I~were
2-
pcr2 s,C”2
are
MO-MO
02s2 Z-866(3)
s4 2.855(l)
Mo==O,S
1.659(30)
Z.lOS(av)
Mo+S
2.334(14)
2.313(2)
l-lo-s
Z-404(13)-2.418(11)
2.381(2)-2.412(2$
was
determined;
[1201.
0.S
H2L,s, MO\,/“O\
Bond
C50)
S
(51)
70
The
interaction
reduced
forms
distance
of
3.02%
observed
in
the
distances
of
were
xanthine was
distances
in
MO-S
=
2.545(2)x
MO-S
=
2.500(2)%
CMoS412-
reaction. the
the
series
assumes
of
is
=
2.418(2),
the
of
the
bond
The
and of
Bond
S4
EXAPS MO=&
iodine an
and
As
fully
Interaction and
A MO-AS
EXAFS.
the
was
Mo=O
interaction
oxidation
eight
forming
forming
in
Bond
a
an
and
Mo=S
disappeared
of
Mo2(Et2dtc)6
coordinate
flattened
cation
with
tetrahedron
elongated
with
tetrahedron
(33))
to
in
with
Mov(S2)(dtc)3 2corresponding [WS41
the
although
a
distances
2.445(2),
gives
However,
detailed
are S-S
=
give
in
description
Mo-S(dtc)
of
=
2.022(3)%
C701.
almost
are
the
in
certainty isomers
Their -1
IR
identical
W=O in
bond the
dissolve
in
PMe5)
in
small
number
which
one of
such
MeCN
contrast
form
by
bond
=
compound between
oxidizing
and
seems
to
M(III)
been
prepared
blue
and
green,
about
to
give
blue, the
stable
the
similar in
are
group
blue
and
yet
well
c921.
of
isolated
differences and
with
Interestingly, solutions
complexes
This
solution. not
(53)
determinations
green)
green
=
oxidation
been
only
C1241.
MoOC12P3
L
stretching
The
l-893(20)2
0x0
in
by
structure
tungsten.
atoms.
complexes.
have
W=O
diamagnetic metal
(where
shown
favour
have
crystal
structure
is
-trimethyl-l,4,7-triazacyclononane
L
is
always
1.706(6),
the
LW(CO>,
scheme
A
the
reaction
trams
which
(52).
overall
isomers,
to
in
ligand
N,N',N"
(1.719(18)
to
The
shown
The
single
[L'MOX21+
predominates
isomers
a
observed
geometry
distances
is
differ only in their -1 green) and crystal
960cm
faciaz
dry
in
interconvert,
spectra
distances
W-N
to
Two
blue,
scheme
states.
0 1(ClO > .2H 0 confirmed 24 42 2 are MO-MO = 2.586(l), Mo=O
with
compounds
[93,94,1241.
(980cm
showed
the
chemistry
oxidation
2.265(4)-2.346(4)A.
is
and
of
(I,) have
MO
consistent
pentavalent
EL1WOC121+.
frequencies
=
1,5,9-triazacyclododecane
reaction 2
substituted
different
compounds
the
chemistry
highly
the
a number
anti-CL
MO-N
is
different
containing
distances
and
distance
more
in
geometry
scheme.
MO
metal
1,4,7-triazacyclononane)
not
the
coordinate
MO-S2
with
Rather
for
eight
given.
= 1.952(3)(av) the
L'MX3
of
(shown
not
determination
in
CL')
by
set
was
complexes
facCaZ
a
structure
MO-p0
the
MO no
tetramethylthiuramdisulphide
product
Mo(S2)(dtc)3
prepared
shown
form
As
by but
and
[1211.
showed
set S4
or
reduced
CompLezes wiS-zn
A
and
with
W(VI)
2.496(2)-2.553(2),
been
MO
reduced
prepared
other
studied complex,
either
suggested
one
partially
[1223.
stereochemistry
z .2.4
sets, the
reacts
to
been
MO(V)
determination
two and
the
been
A structural
toluene.
contrast
In
has
the
from
was
oxidized,
have
for
form
interaction
MO-S
with
oxidase
found
oxidized
[Mo(Et2dtc)4113 in
arsenite
unaltered.
a MO-S-AS
and
of
example
understood
(P
which = PMe2Ph,
adds C1241.
to
the
less the do
71
LMo(co13
1
LMo/o>M*L
and
ITo 0
II 0
q.pa-
yellow 2+
(52)
+2H+
-2EI+
H2°
LW02Br2
I I LW-o-WL
)
I \I 00
I
2+
0 00
HN03
Lw(co)j
Br2
I [LWOBr2]Br
0 LW< >wL II O II 0 0
H20
I
H20,Zn/H+
green
argon
solution
I
O2
L I 0L;/“\i
[
‘0’
y-0
I 4+
*
I
2+
0
L$.o.wL
O2
[
(53)
.O/
1 2+
II 0
Reaction 180°C
gave
square the
of
Mo(C0)6
phthalodinitrile
oxophthalocyanato
pyramidal
0x0
with
MO(V).
geometry
group_
Bond
with
the
distances
are
A MO
in
crystal atom
Mo=O
toluene
structure
0.69%
out
= l-668(6)
in
a
sealed
tube
determination of
and
the
MO-N
N4
at
showed
plane
a
towards
= 2.068(6)-2.112(7)%
c1253.
2.3
MOLYBDENUM(IV)
2.3.1
HaZides
AND
and
ha20
Interaction (norbornene, A
theoretical
been
in
early
transition
by
a
of
of on
interaction
disulphide
confirmed
or
WC16
with
gave
crystals
the
carried
terms
conclusions
The
The
MoC15
study
has
symmetry
=3h general
compZexes
cyclooctadiene)
[Mo~S~C~~]~-
the
of
TUNGSTEN(IV)
a
out
role
metals
+
bridge
was
0
and
of
in of
the
presence
B-electron
it
explains
and
treatment
capping
ligands
2SH
and
MoC15
dichloromethane
(S2P
is
from
idealized
leads in
gave
CC13~~(~2)C12~~C1312-
-
identified
crystallographic
in
by
study
IR
and
+
spectroscopy the
to
some
clusters
of
is
the
reaction
2~~1
(vS_~
structure
= 609cm
shown
in
-1
> and
(54)_
2-
(54)
\,I
Cl
If
cluster
distortion
The
Cl/ ycly distances
olefin
[1261_
,fl\ Mo/iAMo/y, Bond
an
(MO 111)2M01V
the
distortion_
bridging
of
MC14(Et20)2
c1271.
NEt4SH
(MoC$)~
2
trinuclear
Jahn-Teller
the
of
Et
are
MO-MO
=
2.763(2)
MO-Cl
=
2.393(3)-2.416(3)
regarded
as
a
single
MO-S
ligand
MO-uC1
the
geometry
=
2.435(4)
= 2.468(3)%
of
the
molecule
is
almost
73
ideal
for
single
two
bond
electron
2.3.2
face
and
with
g5Mo
The
of
nature
NMR
They
recorded_
the of
on
spectra
of
are
donor
atom
donor
a
a very
signals
magnetic
metal
oxygen
cover
the
the
each
properties
is are
consistent
with
consistent
with
a one
11281.
large
number
range
extremely the
of
of
Mo(IV)
chemical The
broad.
on
distance
ligands
wide
ligands
MO-MO
The
octahedra_
interestingly
localized
Complexes
some
sharing
complexes
shift
effects
linewidths
and
have
(61035
of
to
been 63180)
and
stereochemistry
and
shifts
discussed
chemical
are
the
c1291, Blue
diamagnetic
compound mole
to
reported
equivalents
showed
it
of
168O_
of
the
more
to
of
The
excess
corrected
rate
the
is
product
thiocyante
been
that as
rate
four
follows:
was
at
1
also
of
oxygen
H20(tra?zs
u20)
a
structure
about
remaining
water
complexes
containing
is
k
the
isotopic
of
the
same
as
in
CNCSI-
to
molybdenum 1,911 (w
and
111)2W1v
shown
in
2M
HCl
give
90°C
=
cluster
with
2.11Og_ like
arrangement %Pr
their
and
it
is
to
amount The
1'
With
statistically
sites
a small l+k
a
studied_
give
of
the
CNCSI-,
aquation
of
the
with
3yrs,
gave 2+
11321,
water
techniques.
molecules
was
It
rates
H20(trans
oxalate
p3 -0
solvent
with
u30)
found
half
about
l_lh
confirmed
Others
cases
and and
[Mo~O~(OX)~(H~O)~~*salt
have
that
prepared
the
the two
Cs3[Mo304(o~)3(H20>3~_CF3S03.3H20 all
lives
and
structure
of
the
anion
c1331.
followed
bond
the
been
and
different
CPt(enj21
to
anion,
(55)
44
very
>
In
[W30,(NCS),15-
analogue W-N
at
four
angles
similarly
equivalent
the
CW3(P3-Ol(lJ2- o),(H20),14+
Orange K2[WC16]
is
to with
have
[NCSI-
With 4+
with
Cs2~Mo304~ox>3(H20)33-4H20.C.3H2C204_ is
eraa-O-W-O
prepared
tracer
at u20
trans
same
with
c1311.
Reaction
was
kltMo304
In [Mo3041
days,
determination
molecule
W(IV)
determination
due
[Mo~O,(NCS>~]~three
=
exchange 5
by
+ k 1_
studi::
oxygen
2omin.
and
sites
was
4+
assuming
/3)[NCS-1
oxygen 18 using 0
about
WC14(SEt2)2
acetylenes
CMo3041
of
25OC
types tJ3
crystal
(k
and
exchange
studied
the
of
used
I
monomeric
structure
1_86g(av)
2,6-C6H3Me2)
first
treating K-ray
coordination
product
[Mo304(%113+
of
=
the
cl301.
the was
=
towards
anation
k
complexes
The has
the
by
W-O
potential (R
is
in
with
unreactive block
constant
constant
prepared
planar
[NCSI',
equilibrium
2,6-C6H3(iPr)2)
was
acetylenes
of of
=
toluene/ether.
W(OR)4
towards
kinetics
large
is
which
analogous
reactive The
it
in
square
compound
The
(R
and
LiOR
almost
phenoxides
groups_
a
he
W(OR),
which
has by was
distances
been
ion
shown W-W
to =
EW304(H20),14+
can
its
analogue
molybdenum
prepared
exchange
be
by
the
separation_ have
the
2.534,
W-u30
reduced
to
(1341.
same = the
hydrolysis It
reacts
structure 2.039,
W-u20
corresponding
of with as =
its
74
H
2
2
Bond
distances
for
the
triflate
The
2.491(l)
MO-~30
=
2-01(l)
MO-0(H20)
=
2.15(l)
MO-U20
=
1.908(2)
MO-0(0x)
=
2.102(8)x
compound
~W302(OAc>6(H20>(OH)2~.16H20
isostructural
between salt
with
water CW
0 32
detected
and
hydroxy
the
shorter
dependent
than upon
W-H20 in
and
evaporation was
characterized
trinuclear each
edge
corners the
the are
crystal
X-ray
with
metal formed
the
6
P 3-O The
by
H-bonding
strong
H302
2
and
disorder
in
of X-ray
OH
KBr,
the
to
crystal
double
diffraction
ligands
almost
found the
as
suggesting
could
short
be
as
that
the
this
W-OH bond
c1351. in
dilute
KCNS
0)(H302)](NCS).H20 The
oxygen
triangle.
is
cation)
(H
diffraction.
two
and and
lattice
dissolved
prepared
atoms groups between
structure
solution
and
crystallized is
the
usual
and
two
acetates
bridging
link
the
clusters
at
OH
on
one
out
cluster
two and
H20
C1361.
Interaction extensive
by
aquo
in
is
presence
H20
distance
tris
was
that
[W302(0Ac)
complex
arrangement of and
other
the
the
crystallizes
bond
the
been
There
in
so
H-bonding
CW~O~(OAC>~(H~O>~~(CF~SO~)~ after
has
analogue. However
groups-
However,
(and is
molybdenum
(H 0)(OH)2].K3r_15H20 6 2 disorder in this crystal
distinguished.
length
its
(OAc) no
distance
are
=
MO-MO
be
complex
workup, structure
of a
and
W(CO14(pip12 low
yield
determination
of
the for
HOAC/acetic
anhydride
bromide
showed
a
after
gave,
cluster.
CW30(CMe)(OAc)6(H20)312+ the
mixture
stereochemistry
A
on
75
similar were
to
those
disordered.
but
may
be
and
one-electron
of
The
W-W to
+2
of
cation
the
Electrochemical pairs
of
amounts
CM0~04(cys)~l led
Individual
of
+l
of
reactants
is
pH
+I
dependent
Th e
cation
is
but
sharp,
fast
the
cluster
is
The
cluster. equilibrium
electron
+l in
The
electrochemically-
subsequent
but
species,
2.801(1)~.
diamagnetic a
observed
slowly
is A
'H
NMR
formation could
of be
is and
all
eLght
separated
consistent the
general
possible by
only
ion with
scheme
exchange initial envisaged
due
at
a
formation [1371.
-0.95V 2in
vs
NHE
of
equimolar 4+ .
[Mo~O~S~_~]
_ The
techniques
of
formation is
of
to
them
in
shown
the (56)
cub ic for
C1381.
CMo3041
0
slowly reversible
spectrum
between
triangulo
groups
paramagnetic,
cation
broadens
exchange
capping
solution.
reduction at a mercury pool electrode 2_2and CMO~O~S~(C~S)~I , CM020~S(cys)~3
products 5+ [Mo~O~S~_~~
compounds pair
the
complexes
distribution
one
to
trinuclear
distance
is is
and
bicapped
the
there
couple
solution
the
other
reduced
re-oxidized
fresh
of
4+
0
II ,
I
O,
MO
MO 'SI
CMo302S21
4+
(~-01
CMo302S21
4+
(Q-S)
‘S’
--+
(56)
CMo3S41
4+
76 2.3.3
Comptexa
with
Addition
suZphur
donor
Zigmds
of MoCl 4 to two mole
equivalents
2,4,6-triisopropylbenzenethiolate) reduced
to Mo(SR>4
crystallography slightly number
which
WC14(SEt2)2 showed
with
it to be
geometry
thiol
tetrathiadecane)
by
an analogous
complex
MoC14(thfj2
and
the
structure
of
oxygen,
but
X-ray
by
the
to be a
forms
a carbonyl
X-ray
is rapidly
molybdenum
compound
prepared
of NEt3_
It
a
adduct
was
interaction
of
crystallography
molybdenum
compound
with
cl.301.
(dttd
= 2,3,8,9-dibenzo-1,4,7,10-
PPh3
formed
+
latter
MoO(dttd)
the
by
+ 20-MeSC6H4SH
the
was
planar
(17)
The
isolated,
corresponding
+ PPh3
was
be
square
Mo02(dttd)
Mo02(dttd)
and
the
and
and about
= 2.262(2)x.
presence
with
is reduced
to moisture
W(SCMe3)4
in the
tetrahedral compound
could
(SR =
MOOCH_
stereochemistry
MO-S
[1391_
isomorphous
Mo(VI)
with
which
isolated
the
between
The
adducts
to be
the
of Me3Si(SR)
surprisingly,
sensitive
showed
tetrahedron
of acetylene
too unstable
is very
on Mo(SR)4
flattened
gave,
+HO
compound
+ PPh30
reaction
MoO(MeSC6H4S)2
-
2
was
determined
and
is shown
in (57).
0
(57)
Similarly tridecane compound
the pentadentate (H2L) MoOL,
Reaction
reacted whose
an
are
MO-P
interesting
is thought
that
MoC14(thf)2
in the
is shown
in (58)
and
with
the
MeCN)
with
structure
the phosphorus
= 2_472(10)(av)
contrast S-S
with
enzo-1,4,7,10,13_pentathia-
2,3,11,12-dib
(L = PPh3,
compounds
to be octahedral
distances
with
structure
of MC14L2
MEPhP(CH2CH2S>212 shown
ligand
and
MO-S
MoCS(CH~CH~S)~I~
interactions
tend
presence
of water
PPh(CH2CH2SH)2 of
atoms
the
gave
the molybdenum C&T
to each
which the
was
Bond
The
compound
is
prismatic,
It
is trigonal latter
compound
other-
= 2_348(12)~(av).
to favour
to give
c411.
and
the
introduction
77
of
the
two
favour
of Two
phosphorus octahedral
new
structures
the
bmpd-
former
with
n
series
= 2)
while ligand,s
series
there
are
structures Reaction
each
nitrogen the
nta
feature u2-s
dmf
of
the
are
gave
six
the
second
give and
ligand
shown
compounds
and
two
(se-613
mpd-
(60)
the
only on
basis with
nta
carboxylate
of
reaction
be
the
five
balance
For
the
of
their
conversion
the
in
36OMHz
the
were 'H
stoichiometry
In in
NMR
crystals
the the
to
one of
trianion
the
original
first second
isolated
and
spectra
cl401.
acid
(H3nta)
of
consists
purposes
the of
and
(61)
nitrilotriacetic
structure
the
types
isolated
the
while
compounds
workup)
in
of
and
compounds.
coordinated
present
W(IV)
for
chelation
excess
The
oxygens. to is
the
.
All
protracted
ligands
of
prepared
stereoisomers
gave
rings.
(after
assumed
tips
mpic-
rings
S),(nta)(ntaH>,l.
is
this
on
been
in
(two
series
5 membered
tridentate
sphere
complexes
have
4 membered
afforded
ligands
c1411.
chelate
(NH4)2[Mo3S13j.2H20
(NH4)3[Mo3(u3-S)(~2with
mixed
determined of
refluxing
4
coordination
[gOI.
(59)
both
in
the
W(bmpd)x(mpic)4_x
ligands
series
their
of
and
of
into
geometry
series
W(bmpd)x(mpd)4_x
The
atoms
of
the
Mo3S4
molybdenum charge
form.
balance The
IJ~-(S~)
core
through one
interesting group
to
of
78 Electrochemical -O_85V ion On
vs
NHE
at
exchange
a mercury
separation
addition
The
reduction
of
structures
pool
Na2[Mo202S2(cys)2]
electrode
procedures,
CNCSI-
they
of
cations
the
gave
gave
gave the
are
in a
green
given
4+
and
[Mo~S,(NCS)~]~in
(621
and
HCl
under
solution
[~03~4(~20)91
known
2M
at
which,
after
CMO~S~(H~O)~~I~+_
and
(63)
H2
cMo4S4(NCS)12]7-.
E1421.
I’
I MO/S\
\
of
‘l\/y
s\I/s
‘I’
(62)
MO
(63)
‘I’ Reaction hydrolysis and
a
and
second
identical provided whose was
by
shown
grossly
the
to
be
2.3.4
acetic
whose
visible
(I).
isolation
of
was
determined
due
to
the
change which
is
the
with
of
investigated.
All
stoichiometry
of
4-MeC6H40H
Mo(NMe2)4
the and
and
with
products
to
be
geometry
of
this
products
coordinate
similar of
4+
(I)
but
not
[Mo3S41 to,
was
[Mo3S414+
band
structure
[144].
The
of
(II)
the
structure
is
a
and
the of
publication, and
2.791(l) to
to
by
Cs2[Mo3S4(ox>3(H20>3].3H20
reported
presence
2.869(1)?~. It was 4+ by air oxidation [Mo,S,]
coordinating
ligands
(such
as
donor 2 igands
phosphorus
series
alkylated
of
paramagnetic
depended
2-tBu,6-MeC6H30H
were
identity
isolation
=
due
followed
cl441.
a
3,5-Me2C6H30H
five and
the
were
trans. Mo(OAr)4(HNMe2)
presumed
2,6-zPr2C6H30H
in
spectra
the
reflux
bands
subsequent
converted
trimer
nitrogen
the
MO-MO
slowly
the
a
was
with
accelerated
stabilize
CO?RpZexces
Reactions
type
WV
complex In
under
green
of
oxolato
[1431_ 6+ and
[Mo4S43
is
and
Confirmation
of
cubane 6+ [Mo4S41
anhydride
yielded
(NH~>~EMO~S~(NCS>~~I_~OH~O
that
the
oxalate)
and
separation
(II)
that
distorted
observed
With
exchange
product
structure
Na2S
Mo(COj6,
ion
with,
derivative
and
of
upon
the
species gave
were
obtained is
not
phenols
have
been
= l-10-1.79BM)
steric
the
products was
(u
demands
but of
the
Mo(OAr)4(NMe2)2 with
known.
The
alkoxide.
which
2,6-Me2C6H30H
Mo(OAr>3(NMe2)(HNMe2)
the
sterically [1451.
but
were the
demanding
79
cwp&q in
scheme
(L A
(63).
indicated Bond
4+
in
the
distances
=
1,4,7-trlazacyclononane)
crystal scheme
are
=
[92]_
The
N,N',N"-
compounds
of
the
type
crystallographic distances
MO-N
The
tridentate W-u30
by
confirmed
of
as
confirmed
coordinated =
also
=
with
in
of
manner. W-N
and
gave
L'MoBr3.
2_365(4>-2_458(3>%
=
Mo(IV)
A the
ligand.
1931.
Bond
Stmilar
C941.
N,N-bis(5-*
(64)
1.94
(L') of
earlier
structure
a facial
W-u20
oxidation
=
indicated
the
in
2.10(av),
fffcidcoordination
Mo-Br prepared
W(CO>6
(H2-L2-Lv2)
mild
the
2.237(13),
were
reaction
diaminobenzene
determination
2_52(av),
[L'MoBr31+
=
complexes
the
isolated
trimethyl-1,4,7-triazacyclononane
study
are
tungsten
with
W-W
2_14(3)-Z-26(3)2 ligand
structure
was
dry
Bu-2-hydroxybenzylidene)-1,2-
mesitylene
Me
at
170°C
gave
a very
complex
Me
(64)
mixture four
of
more
species
than
have
coordinate
W(L2-LU2)2.
identical,
but
signals
indicating
a
of
WH5(PMe3)3M'_ ether
determined. the of
the but
potassium
hydrides
are
two
are
extreme
of
H
IR
spectra
5
case the
salt
of
directed of
for
of
which towards the
of
are
achieved
of
the
the
four
different_
by
TLC
neutral
isomers All
are
showed
with
no
Inherent
symmetry
or KH
in
thf
yellow
and
eight almost bl3U
four
and
possible
[146]_ NaH
X-ray
> M'(crown) 33 the sodium
geometry for
spectra
complexes
was
stereoisomers
NMR
with
(PMe
separation
as
and
suitable WH
views
Partial
discussed
Crystals
In
the
set
WH6(PMe3j3
adducts
analysis, the
36OMHz
were
Reaction
species_ characterized Visible 1
their
stereochemistries
crown
15
been
the
all
diffraction and
salt,
bonding
structures
the
hydrides
as
shown
in
two (66)
prepared of
was
Ligands
and
compounds
and
not
(66)
were
detected
observed.
from
the
adducts
identical
were
away
for
both
were
fragment
hydride
potassium
were
the
W(PMe3j3
the
gave
potassium_ [147].
to
in that
Three There
of
80
_ PMe3
PMe3
“,,,\
0
1 /H -
-
along
the
analysis
lithium
simiLar
to
that
of
A
crystal
the
terminal
Me
from
tungsten of
the
Na
nBuLi
square long
hydride and
and
K
gave of
(66)
and
the
[WH5(PMe3)8Lil4
tungsten
short
ligands,
atoms
Li-W
it
is
arrangement
salts
WC14(PMe3)5
structure
feature
the
tungsten
in
excess
a
alternating
between
solution
HH/i\HH/K
and
contains
reveal and
Reaction addition
with
not
between
yellow
WH6(PMe3j3
showed
edges
6
\
(4351
between
did
I /” --
PMe3
PMe3
crystallography
Me3P\
0
'0'
HH
Reaction
1
b
K+
HH /;\
0
/
which having
distances. possible
of
the
X-ray
lithium Although some
that
the bridge
fragments
W(PMe5)8
LiAlH4
in
Et20
at
-8OOC
followed
by
NCH CH NMe 2 yielded insoluble Me2NCH2CH2NMe2A1H3 2 2 2 which was isolated (PMe3>3H3W(~-H>2A1(H)(~-H)2tJH3(PMe3)3.
hydrides structure
resolved
were is
not
H
W’
the
clearly
bridging
the
is
11471.
and
determination
atoms
resolved. section
H\
.Al’
‘“‘I
hydrides
attached The
shown
to
most
in
Al,
a
but
the
interesting
(67).
,w
and
The
complex
(67)
\H H
can to
be
considered
describe
it
as as
[AlH5]
fluxional
in
solution
-8OOC
at
this
the
and solid
state
Reaction addition
of
at
with
between CsCl
2-
gave
brfdging
room
temperature structure
CompZexes
2.3.5
a bis-WH4(PMe3)5
adduct two
temperature 1 the H and
of
but
AlH8,
[WH3(PMe3)3]+ but
rigid
31 P NMR
it
on
the
equally
The
units.
spectra
is
NMR
are
valid
compound
is
timescale
consistent
at with
C1481.
mekat-carbon
bonds
NaK3[Mo02(CN)41_6H20
and
Cs2Na[MoO(N3)(CN)41-
A
NaN8
at
pH
crystallographic
9.5-10
followed
study
showed
by a
81 trans
configuration
displaced
N3
ligand
121(61°
is
the are
distorted plane
MO-O
but
linear,
field
KCN by
tungsten
at
the
the
photolysis
the
four
= 1.70(l),
angle
the
interaction
complex
at
anion
cyano
MO-N
with
groups
the MO
towards
= 2.29(2),
MO-C
the nitrogen
bound
alkaline
solutions
atom the
of
presence intensity.
NMR
have
species.
the
signal
given
The
= 2.17(1)x.
to molybdenum
is
structure
of K4EM(CN)81
the pentacyano
MO,
and
complex
but
cyanide,
due
of
on K~CMOH(CN)~I. as
appearing
spectra
a doublet
solutions
that
the
+ OH-
and
The the
not
also
the
but
addition
also
is fluxional signal
showed
of base
determination
reduced
with
KCN
showed
gives
CMO
--L
K5cMo3S4(CN>g].3KCN.4R20
a typical
Nc\
Mo(IV)
trimer
core
and as
a crystal
shown
I /CN
5-
MO
S’I ‘s NC\I /\I /CN Nc~io'S~~~CN CN
CN
are
MO-u3S
its
equilibrium
CN
MO-MO
appears
the
C1511-
of MoS3
distances
was
for
molecule hydride
of K5[Mo(CN)71
to the hydride,
is suggested
in solution
Reaction
For
CMOO(OR)(CN)~I~-
been
spectrum
I3 C NMK
It
of
aqueous
EMOH(CN)~I~-
Bond
0x0
ClSOl-
details
The
82.3.
of
q CMO(CN)~~~-
gave
Further -t_ the l'C
occurs
of
octahedral
11491.
containg
with
of
distances
Ligand
formed
out
0.282
Bond
group.
for
= 2_775(ll)(av) = 2.363(3)
MO-C Mo-u2S
= 2.182(13)-2.222(10) = 2.312(2)-2.324(2)g
(68>
in <88)_
82 The
crystal
paper
Bond
IR,
and
the
The
;*\
S
2_758(7)
=
2.06(5)-2_22(5)2
resonance
the
Raman
anion.
of
former
as
Bond H)
The
also in
iN,
reported
of MO-Cl 3-
=
been
were
8-
CN
to
this =
be
presented
and
active
complex
together
olefin
2.439(2)-2_469(2)A
in
(H 0
the
73 case
)(NMe in
MO-MO
=
and
other
Mo-Br
(NBu4)2[Mo2Br6] the
2.384(4), =
with
course
+
PEt2Ph,
a
detailed
of
the
-
2L
PEt3
or
1/2dppe.
have
epoxidation.
the
A
been crystal
octahedral
Br
8
HI
does
not
structural Mo-uBr
=
2_546x(av)
monodentate
disorder
studies
on
is
addition,
salts
2.630(av),
bidentate as
in
scheme
(70)
(NBu4)cMo2Br5L41
In
in
[154]. and
reactions
show
(NBu)[Mo2Br5L21
-
Mo2Br4L4
PEtPh2,
with
[153].
)CMo
4 2 previous
are
and
2.295(14)
(dppeH2)3[Mo2C1912
in
confirmed
2.635(5) of
=
c1521.
distances
investigated
=
same
(69).
12L
L
the
'CN
(dppeH2)3[MoC1612
(NBu4)2EMo2Br61
where
in
TUNGSTEN(II1)
proved
has
reactions
been
shown
/\*
spectra
AND
[Mo2Br8H1
state
Mo-Br(trans
is
,
CMO~S~(CN)~~I
for
with
anion
solid
anion
MO-S
=
MO-C
determination
The
have
,,/
MO-MO
stereochemistry
this
S
preparations and
structure
the
iN,
analysis
reported
the
NC,
MOLYBDENUM(II1)
2.4
of
was
are
and
vibrational
(PPh4>2CMo2S2(CN)8]_nH20
stereochemistry
distances
Raman
of
structure
the
reaction
phosphines (70).
of
83 (NBu4)[Mo2Brg(dppe)21
was
reported
was
determined
in acetone and
distances
are
2_532(8)2
[1551_
Trans very
structure
MoC13(thf)3. CMoC14py21-
MoC13(thfj3
were
of
(ttt)
The
basis
formed The
readily
complexes
and
isolated
MoC13(ttt). the
are
IR studies,
in reactions
reaction
distances
will
probably
of
other
prove
Mo(III)
stereochemistry
is more
Bond
P> = 2.565(4),
stable
[MoC14(dppe)]-,
was
MO-P
to be
=
a
complexes.
with
MO-Cl
in solution
A
=
than
[MoC14(PMe2Ph)21-
and
W-W
prepared
by
the
and
involved
WC14(SMe212
mixed
cleavage and
Addition
determined
(hto).
by X-ray
excess
of PPh,Cl
of
le\
structures oxidation
were
state
the macrocyclic
Et3SiH gave
diffraction
Among
MoCL3(ttt)(thf)
polymeric
some
of
1,4,8,11-tetrathiacyclo-
(MoC13)2(hto)(thf>,
insoluble
interaction
gave the
and
the
and proposed
compounds ring
51571.
diamagnetic
chloro
is shown
derivative in c71)_
7 <71)
are
H) w-s
hydride
been
polythiaethers
In addition,
which
between
w-cl(trans
The
the It
have
the
MoCl3(hto),
complexes
of
structure
the
and
(NBu4)[MoBr4(dppe)l
geometry-
1,4,7,10,13,16-hexathiacyclooctadecane
were
w-w
of
to give
of
Mo-Br(cis
preparation
confirmed
with
Cl
Bond
the
of Mo(II1)
C13W(u-H>(u-SMe2>2WC12(SMe2). whose
structure octahedral
prepared
= 2.154(12)2.
or MoC13(PrCN)3
tetradecane
on
for
+
[1561-
series
complexes
h as been
MO-O
It reacts
crystal
a distorted
P> = 2_586(4)(av),
material
and
(NBu4)[MoBr4(dppe)l
The
has
determination
2.421(91-2.442(8)
A
anion
Mo-Br(tras
starting
-
solution.
the
-CMoC14(thf)21-
useful
crystal
+ 2NBu4Br
bond
= 2.419(l) = 2_407(5),
W-H 2.435(5)
= 1.48
W-Cl
= 2.375(5)-2.394(4)
- 2,372(5)-2,389(4)x
length
is consistent
is noticable
in the W-Cl
with bond
a triple
bond
distances_
and
The
the wms
hydride
NMR
effect signal
occurs
at the very
interesting rotomeric
variation forms
Crystals mixture the
high
of
of
frequency
with
the
at room
which
temperature
is discussed
and
shows
in terms
of various
Cl581.
(NMe4>[{MoC1Br(02CH))301
shown
is
temperature
anion
of MoBr 3, NMe&Br
anion
of 63.71
and
HCOOH
were
in EtOH
isolated
saturated
from
with
the
HCl.
reaction
The
structure
of
in (72).
Cl
I/ \
0 \
/
MO
‘C
I \
/ B?-
(72)
0
0
\ Cl/ \B/
Bond
distances
electrons and
the
spectra
structure
= 2.&?o(av) = 2.53l%(av)
is similar
to that
of
the
but
formal
oxidation
available
for metal-metal
bonding.
study
The of
distance has
spectra the
the
been
first
is retained
is consistent made
suggested
=
on reduction
state This with
(MO =v> 3,
of that
two were
Mo(IV)
the
almost of
is 3.33, suggests
this
species
identical
(MO Iv13
trimmers with
(MoI1113
latter
1.976(3)
- 2.080(4)-2.098(4)
MO-O
triangle,
A Raman
the
MO-&I3O
Mo-Br
internuclear
solution.
‘Cl
= 2.596(l)
MO-Cl
structure
the metal
/
are
MO-MO
The
I
MO
so there a bond
capping
are
order
eight of
1.33
fl591. and
(MoI")~
has
suggesting
c1601.
a u3-0
a p2-0x0 that
in aqueous bridge the
and
trimerlc
85 Interaction MeOH
in the
isolated
of Mo(NNHPh)2(butane-2,3-diolate)2.H2NNHPh
presence
black
determination
of NEt3
crystals
of
revealed
gave
a deep
purple
solution
(NHEt3>[Mo2(NNPh>4(SPh)53'
the
arrangement
shown
with from
excess
which
A crystal
HSPh
in
were
structure
in (73).
Ph -N
‘“\ /%I\ ph’N-N /Mo \‘/
SPh
N-N-
MO -
S Ph
PhS
Bond
distances
= 3.527(l)
Mo-pSPh
= 2.533(5)-2.653(5)
MO-N
probably
very due
distorted
long
MO-MO
to the
electron
of PPh3 shown
the usual
manner
addition
of
from
CS2
yield
formed
aqueous
mtZ-tL2M02041 the
terminal
confirming LMo(COj3
groups. of
bond
The
reaction
ligands of
the u-n
interaction
ligand
contains [162].
mechanism
of
remain
original 2
between
ligands
the metals.
and
CS
a free
C=S
unit
the reaction
and
(formed which
of green
(L = 1,4,7-triazacyclononane)
oxygen Br2
atoms atom
in the
transfer
in CHC13
gave
product C1631.
are With
monomeric
derived the
same
CLMoOBr2]Br.
in the the
chelating
is modified The by was
is
11611.
has
are
is
unit
CS2
which
of CS2
this
distance with
intact dtc
and
Mo2(SPhj3
the MO-MO
C2S3
in by
ligand
S abstraction methylated
to
diamagnetic with
solution have been investigated. The reaction 2+ 18 quantitatively. By use of 0 enriched N03oxygen
with
dtc
cation
CL(H20)M~(0H)2M~(H20)L14+ acidic
NNPh
extraordinary
is bound
the
This
and
an
fourth
which
corresponding kinetics
Three
the
by
a metal-metal
lengthening
Z-525(5)
= 1.26(2)-l-37(2)8
Mo2(dtc)3(p-CSC(S>S)(~-S3C2NEt2)
(74).
while
by PPh3).
the The
to give
a CS unit
is presumably
the
undergoes
in
precludes
withdrawing of
= 2.449(7),
N-N
distance
aa a consequence
structure
Mo-SPh
= 1.73(1)-1.83(l)
Mo(C0)2(Et2dtc)2 presence
\ N -Ph
are
MO-MO
The
(73) N
from
the
ligand,
nitrate
ion
in
yields it was
shown
nitrate, oxidation
Reduction
of
that
thus of
this
in
86
NEt2 /
s
--A / Mo2 I \
S
Bond
distances
aqueous
(74)
S
are
solution
MO-MO
= 2.616(l)
MO-C1
= l-920(9)
Mo1-C3
= Z-026(8)
Mo2-C3
= 2_086(9)
Mel-S4
= 2_449(3)
Mo2-S4
= 2.406(3)2
by
Zn under
4H20
[Mo2L2(V-OH>(U-Br>Br21Br2. CMo2L2(W-OH>2Br21.2H20.
N 2 followed
The
whilst
structure
by
addition
reduction of
the
of NaBr
at elevated
former
was
gave temperatures
determined
and
gave ie shown
in (75).
-r \ (/ N
N
Bond
distances
The
N
I/ I’
Br
H
MO
(75)
/ Br
are
MO-MO
= 2.558(3)
MO-N
Mo-Er
= 2.547(7)
Mo-uBr
MO-POH
= 1.84(2)x
short
MO-MO
separation
indicates
strong
= 2_19(3)(av) = 2.558(5)
bonding
and
a triple
bond
is
87 suggested
The
c1641.
similar
with
bond
and W-N
= 2.2O%(av)
Reactions
structure
distances
of
W-W
= 2.477(3),
of W(N2)2(dppe)2
[W(OH)(NNCMe2>(dppe>2]PF6
with
in dichloromethane
study
EBFI-
2.312(5)
2.5
and W-P
retain
the
a different reacted
that room
the
with
tetrameric
On
n. cluster
re-generates which
product
to
basis
of
[Mo2Br61 2- has 1,2-dibromoethane.
The
on faster at room
are
2/3
rates
temperature
but
(PPh
their
B-MoC12
(PR3
Br\ I /
supports the
two the
Br
C1C6H5
[166].
W-Cl
=
Direct
to
Mo(CO>~ and
gave
AlC13
A spectroscopic
reaction
suggested
with
PR3
at
and
NEt4Br
t1671.
of Mo(CO)6
electrochemical
appear
reaction
Mo4C18(PR3)4
view
interaction
with
S-MoC12.
clusters
the
these and
Mo2(OAc)4
of
this
second
gave
studies
reaction
oxidations.
is irreversible
and
(PPh3Mej2S6 l/3
gave
The
under
in
first
all
mixed
single
is
scan
crystals
(PPh3Me)2[Mo2Br6S2(NO)21
Br
,,\ I /- No
ON/;‘\BrAi ’
1
with
= PEt3,PCPr)3,
precursors
form
clusters.
Me) [MO Br (NO) ] and 3226 4 in (76) and (77) [66].
NO
r
a crystallographic
cl681.
of Mo(N0)2Br2
shown
of
rectangular
by
shows
gave
with
geometry
spectroscopic
a reactive
the
prepared
anion
scan
interaction
of containing structures
been The
and kms
Prolonged
to be
give
with
of W(N2)2(dppe)2
Mo~C~~(PR~)~
arrangement
appeared
product
in refluxing
Mo~CI~(PR~)~.
C1C6H5
this
the
solution
to have
or MOM
also contains tetrameric 2 temperature to give Mo4Clg(PR3)4
conditions
= 2.545(5)
C1651.
6-MoCL
reversible
to be very W-Br
in H20/thf
CWC12(dppe)21+
clusters
MOSCOW
product
of
found
a condensation
Reactions
cation
TUNGSTEN(I1)
in refluxing
comparison
the
AND
rectangular
phosphine
gave
showed
2.563(5)x
E~Io~C~~(PR~)~I
products
isolated.
= 2.522(5),
of
P(nBU),,PMe2Ph)
with
salt
MOLYBDENUM(I1)
Reactions
was
= 2.095(20),
HFeCo3(C0)12
In acetone,
was
HFeCo3(C0)12 the
W-pOH
[923.
[W(OH>(NNH2>(dppe>2][FeCo3(CO)~2].
on
2+
[W2L2(p-OH)2Br21
NO
2-
(76)
Br
whose
88
(77)
L
Bond
distances
are
= 3.978
MO
MO...
=
2.590(av)
MO-N
=
1.837(12$
Electrochemical
studies
CMo(H3{Me2pz}~(NO)12]-
which
which
a
itself
undergoes
Reaction
between and
CM(C0)2(tipt)31X-ray
diffraction
bipyramidal
of
MO-S it
species,
corresponding
other the
reactive
and
and
NNPh
Mo-N(MeCN)
=
2.6
to
PMe2Ph
2.227(14),
series
of
(P-P-P
=
be
two
mole
The
have
equivalents
structures
tridentate either
of
ligand NH3
=
or
also
N-N
products.
showed
distances
are
a
formally
of
could
whilst
be
trigonal
MO-C
CO
=
gave
the
easily
[NNPhlC
in
MeCN
confirming
Mo-N(NNPh)
1.211%
a
14-electron
Addition
are =
gave
similar
determined,
distances and
gave
carbonyl ligand
was
Bond
for
extra
of
C1691.
complex
addition.
carbonyl
2.32(av)
complexes prepared
under PMe2Ph
the
compounds
was
usually
N2H4
the
formation
=
gave the
l-782(12),
[1701.
TUNGSTEN(O)
been
of
Bond
expected
structure
axial.
thiols
axial.
the
2,4,6-%3C6H2SH)
molybdenum
and
but
mono(dinitrogen)
PhP(CH2CH2PPh2j2)
(Htipt
the
.
Mo(HBCMe2pz}3(NO)I(solv)
=
As
MO-S
AND
Mo(N2)(P-P-P)(L-L)
gave
to
form
Htipt
of
one
to
oxidation
substitution
whose
ligands
I-
carbonyls
replace
2_662(av)
showed
demanding
salt
anion,
MOLYBDENUM(O)
A
loses
and
the
2.396(15)
=
one-electron
aterically
with
[Mo(MeCN>(NNPh>(tipt>33MeCN
slowly
PPh4+
=
Mo(HBiMe2pz)3)(NO)12
reversible
tricarbonyl
NCR
removed.
Mo-pBr)
2_317(5)-2.342(5$.
=
is
on
McCO)4Br2
structure
1.96(av),
Mo=S
Mo-Br
c1711.
by
limited or
one
were bound
Mo(N2)(P-P-P)(PMe2Ph>2 Na/Hg
mole
of
determined in
reduction
amounts
a facial
of
L-L by
of
nitrogen
(L-L 31
manner.
=
or MoC13(P-P-P) in
the
presence
of
dmpm,dppm,dppe,diars).
P NMR
studies
Reaction
and with
the acids
HX
89 Reaction
of
WC14(PMe3)3
> (PMe > which reacted 22 34 X-ray diffraction W(N2)(PMe3)5_
with
Cis-W(N
2_04(2), by
W-P(tzwzs
both
N)
complexes
to
a Na
with
give
further
of
the
2.473(4),
=
dispersion
carbonyl
PMe3
latter
other
under
gave
W-P
and
in thf under
=
Ar
bond
at
40-50°C
distances
2_444(7)s(av)_
acetylene
N2,gave to
W-N
Various
derivatives
were
give
= reactions
described
[172]_ The
complexes
cis-W(N2)2(dppm)2
prepared
by
reduction
presence
of
the
also
reported_
2,481(l),
of
phosphine. Bond
N-N
=
The
trans-W(N2)2(Ph2PCH=CHPPh2)2
WC14(Ph2PCH=CHPPh2)2
crystal are
1_123(4)S\(av)
structure
W-N
=
of
1_983(3),
Mg
in
thf
in
the
cis-W(N2)2(PMe2Ph)4
2.015(3),
W-P
=
was 2.444(l)-
have
and
been
recorded
assignments
over
made
for
a wide
the
temperature
lowest
lying
range
excited
C17741. The
single
diastereoisomer
tmns-M(N2)2(S,S-chiraphos)2
(-)(2S,3S)-bis(diphenylphosphFno)butane) form
by
were
[173]_
data
tirans-M(N2)2(dppe)2
states
or
distances
Photoluminescence for
WC16
and
reacted
MoBr(NNCH(Me)C6H13)(S,S-chiraphos)
enantiomer
over
the
other. to
*rans-Mo(N2)2(dppe)2
in
Several
form
with
which
racemic
there
1,4-dihaloalkanes
corresponding
(S,S-chiraphos
was all
cyclic
=
2-bromooctane a
10%
excess
reacted
to of
one
with
dihydrazido(2-)
complexes
c1751.
2.7
METAL-METAL
2.7.1
Tr
Two
and of
bonded
reviews
One
year.
Cl761
compares the
triple
their
bonds The
As
metal-based only
two
valence other as
with
those
of
in
M2(0Rj6
the
triple
in
bond
spectrum
The
The the seems
close
on
triply
have
bonded metal
to
band
this
appeared
dimeric
oxides.
in
alkoxide The
compounds
one
CEC,
the
last
compounds
other
with
distance
a
and
not the
the
x
complexes due
turn
is EN
review and
overlap outer
ionization
as o
ns
might
CEO
and
and
not
much
I
bond
distance
a weak close
npz this
contact
its
higher
of
between orbitals repulsion
expected_
that
been
and
repulsion
be
so
the
the
reduces
Level
d
only
in
and
core
electron
increase valence
that
lie
have
the
implies
result
G
to
suggesting in
the
valence
does
to
sharp
substantial
destabilize
proximity
Is
M2(0R)6
observed
which
metal of
of
are
unexpected
causes
Lonization M-M
u
a number
bands
ionization, of
which of
of two
before,
origins
orbital
occurs
chemistry
structures
slightly
ndz2
also
of
of
noticed
atoms
a result
area
c1771.
metal
effect
this
review
of
The
metal.
of
and tungsten(.Tll)
a general
ionizations_
interactionthe
aspects
photoelectric
reported_
changes
species of moZybdenmIIIII
on is
reactions
SPECIES
BONDED
the of
the and
This
ionization as
previously
predicted.
species
Thus
may
the
also
A disagreement has
been
and
structures Also,
of both
of py.
described
compounds
of
X-ray
analogue
been
from
quadruply
existence
does
. of W2(OzPr)6py2(p-CO)
exist,
reported
but
before
W~(O'BII)~
and
and
and
CO with
isostructural
dimeric
bonded
C1781.
with
in
solution
is
it
and
py_
The
are
now
confirmed.
or without
the
the previously
[179].
with
W2(Ot-Bu)6
diffraction
the
to CW2(OzPr>,py(u-CO)12
have
is formed
on the
compound
It is isomorphous
molybdenum
ReactFon
BuOH.
the
converted
in
o ionization
literature
appears
W~(O'BU)~(~-CO)
presence
t
It
irreversibly
ionization
to the
in the
resolved.
rapidly
sharp
'extra'
be assigned
pivalic
showed
the
acid
(tBuCOOH)
structure
in
gave
(78) with
W2(02CrB~)~ five
and
oxygens
in
(78)
Bond
distances
are
w-w =
2.2922(8)
W-Occhelate
piv)
= 2.138(7)-2.164(7)
W-O(monod.
piv)
= 2.072(7)8
W -.. 0 = 2.53(av)
eclipsed metals is
and
two
similar
temperature the
both
of
to
are
that
to
the
rigid
monodentate
complete
ligand is
exchange not
metal
the
metal
except
W-W
rapid
bond.
mixture
as the
bridging
Two
each.
is
In
of
of W2(02CtBu)6
but
and
atoms.
there
W2(02CNMe2)6
structures
are
one
and
as an equLlibrium
isomers
isomers
of
tungsten
but
ligand
across
betyween
the
chelated
this
trans
state
solid
the
monodentate,
oxygen
ligands
about
are
essentially
second is
pentagons
a
the
that
in
and
on
for
each
on
NMR
tlmescale
bridge
metal
most
likely
increases
At
but at
the
At
the structure
bridging
exists
at room
corresponding low
higher
interconversion
80°C
the
pivalate
The
exchange
metal-
even
final between
compound
W2(02CtBu)6
W2(02CNMe2)6.
isomer,
the
position,
this
each
between
interaction
axial
isomers,
occurs the
each
weak
solution
temperature ligands
On
long in
pivalates
[180].
to
temperatures
occurs temperature, between
91 The
comproportionation
(0R13k4EM(0~13
has W3
been
used
compound
for
+ (oR)~Mo
to prepare
showed
reaction
Wj
and
+
W2Mo
its structure
A crystallographic
clusters.
to be very
similar
to that
study
previously
of
the
reported
its molybdenum
analogue Cl811. . and @BuO) of W2(OzPr>6py2
ReacFion
The
W3(CMe)(OzPr)9. synthesized is shown
from
in (79)
isomorphous
('BuO)~WECM~
Bond
distances
= 2_74(l)(av)
w-o
= 1.90-l-93
of 4-MeC6H40H
paramagnetism, signals,
but
although
Mo2(NMc2)6 structure
in the was
obtained
determined. alkoxides
NMe
the
structure
MO-N
distance
of 2.242
this
of NHMe2
shifted. gave
determined.
However,
this
(OAr)
the
2 4 confacial
the NMe 2 groups
gave derivative
the alkoxides i s very
confirms
similar
the
was
acting
acting
The
mainly
a few
reaction blue
crystals
) 22 2 bioctahedral
(NMe
)(HNMe
ligand
is an
as the bridges.
of another
its
were
was
with
terminal
with
but
product
structure
arrangement The
Me
of 3,5-Me2C6H30H
Mo2(0Ar)4(HNMe2)4
whose
as
to that
is a small temperature dependent 1 H NMR spectrum showed four different the
contact
MO
Mo2(NMe2)6
the 4-MeC6H40H with
of 2,601(2)x
and
has
of
arrangement
not
was
with
distance
were
presence
= 2.02-2,062
bond
-_ There
2 despite
they
It also and
the W3 complex
= 2,06(l)
W-u0
or 3,5-Me2C6H30H
and
groups. The MO-MO 3(2.66%). The in CMo2C19] amido
w-c
bioctahedral
bridging
not
of
/OR
W-W
to be a confacial
and
structure
C1821.
(NH2Me2>~Mo2(OAr>,(HNMe2)21
amine
The
Mo2($Prj6_
are
Interaction
shown
solution gave WECMe in hexane/zPrOH 3 was metal complex MopW(CMe)(&Pr)g
mixed and
,,\
also
M3(~3-O)(~3-OR)(~2-O>3(OR)6
two
amine
groups
92
are
-&as
longer
to
the
than
Mo-HNMe2
NMe 2 bridge_
typical
bond
length
corresponding
to
of
1,2-Mo2(0Ar)2(NMe2)4, NMR
spectrum
structure
in
three
types
being
gauche
bond
were
transfer
Me
to
determined
single
type
of
to
type
complex.
of
higher
but
not The
is
known
that
study
of 1
H
the
NMH
between
material
is
with
of
for of
the of
in
usual
Mo2(0Ar)3(NMe2)3
unique
groups
rotation
shows on
about
and
The
ethane-type
each
the
metal
Mo-NMe2
spin-magnetization
shown
the in
and
showed
the
between
isolated been
and
in
solid
state.
of
NMe2
to
and
addition,
small
the
carbon The
Me
and
This solution
of
at
w4
in
this
-20°C,
but
groups
%PrOH
and
the
of
occurred,
(>>6
equivs)
a black
is by
NMR
by
X-ray
butterfly
(80)_
c’
is
[185].
6366.8ppm)
skeleton
ethane
bonds
rigid
amounts
reaction. in
typical
triple
be
groups W2(NMe2j6
M2(0Ar)2(NMe2)4.
2.2198(141x
distal
between
from
the of
for
compound
characterized
carbido
showed length
typical
proxima
types
but
bond
gave
w*
\-
distances
the
2.4139(6)x
the
compounds
compound
MO-MO
reaction
has
groups
M2(NMe2)6
material
the
were which
OZfr
The
w,’
Bond
is
than
give
temperatures
molybdenum
different
W4(H)2(O'Pr)14,
different
2.11%
1,1,2-Mo2(OAr)-,(NMe2>3'
is
that
energies
to
studies
to
crystallography
whilst
coalescence
exchange
product
be
is
to
expected
consistent
starting
major
crystalline
structure
on
the
W4(C)(NMe)(OiPr!12 (12
from
hexane
product
as
Activation
structure-
temperatures exchange
in
the
form
is
distance
of
shorter
C1841.
gauche
similar
at
both
bond
is
2-t Bu,6-Me-C6H30H
crystal
staggered
benzene
and
other.
techniques
Addition A
signal
each
length but
C1831.
Mo2(NMe2)6
rotomeric
bond
(l-90-2.00%),
Mo-MO
2.5
Mo2(0Ar)2(NMe2)4
gauche
the
The
in
Ma-NMe2
lengths
of
with
but of
of
2.26%.
reacts
bridging
bond
order
a bond
2,6-Ph2C6H30H
'H
The
terminal
w3
are
Wl-w3
=
2.799(2)
WI-w4
= 2_814(2)
w2-w3
=
Z-822(1)
w2-w4
= 2_747(2)
w3-w4
=
2.795(Z)
Wl-c
=
1*914(14)
w2-C
=
1.956(15)
w3-c
=
2_251(4)
w4-c
=
2_241(14)8
spectroscopy
type
93
. OZPr O'Pr
All
five
and
the other
groups The
between
edges
per
of
the
butterfly
(spanning
tungsten
compound
are
WZ-W4)
atom
bridged
is the NMe
four
group,
There
are
of
three
them
terminal
C1861.
Mo4(u3-N)2(u2-OZPr)2(O~Pr)10
(tBu013M0EN
by a u2 group.
and
and Mo2(OzPr)6
was
isolated
its structure
is
as
the reaction
from
in
shown
OR OR
OR
M3’\ I /
RO
OR
N3/Mo’ ‘\ \ I
RO
\
OR
iPr
R=
MO’
OR
/+
(81) OR
RO OR
Bond
distances
are
Mel -MO1
’
Mel-N3
The coplanar
and
and
two
species
= 2,918(l)
Mol-N3'
= l-996(2)
Mo2-uOR
= 2-058(2)x
= l-841(2)
Mol-uOR
I 2,139(2)
the
nitride
long
Ho-N
about
bipyramidal
distances
reaction
W3(NE~(OzPr),,-
isomorphous
oxygen
atoms nitrogen
(excluding
corresponding
of
the
bridging
is T shaped, any
MO-MO
to single
alkoxides The
geometry
bonds)
with
double
bonds
W2(0'Pr)6py2
gave
and
two
are
all
about short
[1863.
analogous
structure
and
stereochemistry
is trigonal
respectively The
Mel-MOP
2_034(2)
Mo2-N3'
molybdenum,
molybdenum
I Z-552(1) =
with
the
with
between
X-ray
imido
.
and
W30(OCPr),,
(‘BuO)~EN
and
the
imido
diffraction showed the usual bicapped triangular * OzPr groups being the caps. The compound is
one
but
the W-W
distances
are
longer
at 2.556(2)x(av)
94 0
compared
with
2_541(3)A(av)
not
detected
in
its
presence
[187].
It give
was
reported
nitrogen
been
in
the
X-ray
0x0
The
by
working
at
crystallography
and
it
Although 1 IR and H
for
1984
that
the
anion
of
with
oxygen_
complex.
analysis,
review
and
isolated
the
crystallographic
(OR>2M(PhNC(OR)O>2M(oR)2
through now
the
for
intermediate low
has
PhNCO the
with
temperature.
the
central
core
NMR
Fmido
with
carbamatoester one
has
shown
proton
spectra
reacts
only It
the
confirmed
M2(0Rj6
in
to
bridging
bridging
been
was
PhNCO
has
characterized
by
(82).
Ph OlC-N /
(82)
Bond
distances
the
-
(RO)3W1
=
CMe3
W2(0W3
are
w-w
Reaction
R
\I’
with
=
2.488(l)
Wl-c
=
2.17(l)
W2-C
=
2.24(l)
wl-0
=
2.255(9)
W2-N
=
2.15(l)%
PMe3
structure
gave
very
in
(83).
shown
unstable
which
W2(OtBu)5(PMe3)[v-PhNC(OR)O]
has
OR
I 0
RO’
The
data
set
product
suggests
through
an
/c\N/ph OR
1
I’
OR
PMe3
was
not
good,
that
the
formation
intermediate
of
the
but
same
w-w
OR
= 2.358(2)%.
of
the
type
product
with
The shown
monodentate
isolation in
of may
proceed
instead
of
(82)
PhNCO
C1881. Interaction temperature
gave
of
W2(oZPrJ6py
W2(OSPr)6(py)(p-P2)
2 with
Co which
2
(CO)8(u-P was
3 in hexane 2 characterized by
this
at
room
X-ray
PMe3
95
The
diffraction.
central
pseudotetrahedral
unit
W2P2
is
shown
in
(84).
/s;-e\ /tip;
py\
f&84) ipro/w \ %,/ ”\oi;rpr
iPrO
Bond
distances
-
are
w-P f 2_45(2)(av)
w-w = 2.695(l)
w-PO = l-989(6),
w-o = 1_892(7)-l-932(7)
2.074(7)
P-P = 2.154(4)x
turn
The
structure
are
related
reLationships
that
form
stable
they
to
analogous
to
that
CO~(CO)~(V-P~)
of
and
have
phosphine
ligands
1:l
adducts
the
structure
L-L
(L-L
shown
in
types
in
isolobal
monodentate
dmpm, 1 H
dmpe) and
31 P
react
with
M2C12(NMe2j4
NMR
studies
suggest
P
I
NMe2 /
W
(85)
Cl ‘I
‘I
NMe2
NMe2
the
by
which
(85).
I
Me2N
=
M2C12(NMe2)4(L-L).
W
contrast,
compounds
CO~
P
In
W2(0R)6(py)(C2H2>
[189].
Bidentate to
is
phosphines
L
(L
= PMe3,
PMe2Ph)
3M2C12(NMe214
+ 4L
-
2M2C13(NMe213L2
2M2C12(NMe2)4
+
--c
M2C24(NMe2)2L2
2L
cause
dissociations
+ M2(NMe2j6
+ M2(NMe216
of
96 (the
second
precipitate solvents
reaction
with
from
reaction
mixture,
disproportionate
further
they
the
PMe2Ph
only).
toluene
4M2C13(NMe2)3L2
The but
M2CL3(NMe2)3L2
compounds
on redissolving
* 3M2C14(NMe2)2L2
in hydrocarbon
+ M2(NMe2)6
+ 2L
600 Crystal CL = PMe2Ph)
structure were
determinattons
carried
out
and
the
on W2C13(NMe2)3L2 structures
are
and shown
W2CL4(NMe2)2L2 in
(86)
and
c1901.
NMe,
Cl I
L
wl Me
Y2\
*N’ I Cl
Bond
distances
CI
PMe2Ph
(87) L
are
W2C13(NMe2)3L2
W2C14(NMe2)2L2
2.338(l)
2.322(l)
WI-N
l-987(7)
l-940(7)
Wl-P
2_515(21
2.534(2)
Wl-Cl
2.457(2)
2.380{2),
W2-N
l-932(7)
l-931(7)
w2-P
2,522(2)
2.526(2)
w2-CL
2.411(2),
EW
=
2-428(2)
2.415(Z),
2.424(2)
2,430(2)x
(87)
97 Using from
the bulky
M2(NMe2)6
structure 2_32(1)g MoC14
in toluene
with
MO-MO
[191]_
The
with
NaSR
to the
2.7.2
have
chemical vary
spectra and
known
quadruple
bonds.
the MO-MO
the resonance
two compounds
of 42.7(2)O
the previously
associated
with
MO Cl (PMe > 24 34 of 8-Mo2C14(PMe3)4 former
are
thermally almost spectral
data,
experimental
There phosphines in all
been
with triplet
leads of
C1961.
spectra
depe
dimers
Linewidths
IR, Raman
containing
skeletal
and
and
MO-MO
stretching
the ground
state
modes
harmonic
dissociation
MO-MO
of O-0978
The
over
than
the 6 bond
energies
of
in l-propanol
the
B-isomer
(NH4)4[Mo2Br8]
conditions,
COS~=~
and
the 6 bond
and
spectral
temperature
above
has
is
compared properties
range system
the ground
and
the
with
the
state.
This
is
eclipsed rotamer. Together with -1 5200cm (15Kcalmol-l) as an
of
the barrier
interaction gives
give
dppe
compounds,
it is paramagnetic
coupled
only
about
the bridging with
B-isomer
chelated
[197].
in alcohols
The major
to rotation
of bidentate
the a-isomer
is obtained
with
torsion
the
of the Dppm
of
prepared.
these
distance
loss
magnetic
component
arphos
from
been with
C1951.
and
of about
in alcohols, and
data
bond
a wide
for
have
stereochemistry
Using
of 40°
a re-investigation
to the reaction
species the
400-500cm*1
to a value
dppe
according
easy
the highest
4148-
electronic,
the complete
angle
lower
In MeOH,
of
the
constants
between that
state
K4[Mo2C181
but
to
and 8-Re2C14(depe)2
examined
with
Interaction
of
Raman
increase
solvents_
ligande,
some
was
Mo(II)
have
3227
an antiferromagnetically
of magnitude
been
from
spectra
is diamagnetic.
bond
has
bonded
of compound
respectively.
a twist
measure
the quadruple
out
the bridging
length
have
this
with
products
of
tungsten~II)
of quadruply
class
force
estimated
which
populated
an order
have
has
consistent
and
M02X~(lI20)~
correlation
a bond
with
=
by reaction
(together the
M L 26
, w-s
c1941.
43.7(31°
is now
8-Mo2C14(dmpe)2
the usual
= 2.312(2)
prepared
of
prepared
[192].
ranging
8-Mo2C14(depe)2 and
and
It
this
Raman
constants,
proposed
revised.
IR and
estimated
isomorphous
number
carried
several
from
are
been
been
of the
The
angles
that
From
were
Separation
derivative
molybdenum,
has
anharmonic
bonds
also
been
[1933.
spectra
and
0x0
was
w=w
Mo2(SC6H2ZPr3)6
of a large
for
study
Raman
located
compound
have
revealed
and
of molybdemm(III
confirm
to 1440Hz
A detailed
the
M2(SR)6
diffraction
= 2.325(2)
prepared.
species
220
resonance
They
of
shifts
frequencies,
the compounds
X-ray
MO-S
molybdenum
similarly
bonded
observed
from
were
same
insolubility
g5 MO NMR
been
at 80°C_
= 2.228(l),
was
&uadrupZe
The
thiol,
in 1,2_dimethoxyethane.
MoO(SC6H2ZPr3)4) due
mesitylene
products
gave
three
were
a-
and
products
98
13-Mo2Br4(dppe)2 respectively, structural and
it
unit
containing The
analysis_
is
the
gave
brown
Bond
distances
the cage.
=
Hartree-Fock-Slater Cr,Mo,W)
to
together
with
the
three
were
the
using
CAS
internal
the
previous
spectrum SCF
is
in
the this
which
has of
could
crystallography,
2_218(1)A). at
The
Ligands 1984. length
to
in
be
X-ray
on
the
force
the
from the
at
Mo2
and
dppe
M2(02CH14
M-M
In
removed
being
the
crystallography.
(M
U,R
or
observed
=
constants
latter
molecules,
6 orbital8
photoelectric
higher
energies
bonded the
quite
contrast
to
earlier
It
is
showed
that
the
than
those
calculated
UV
been
than
the
PBu3
of to
to
in
the
and
suggested earlier
A in
the
molybdenum which
of
X-ray at W-W
oxidation
in
the
which
tungsten
W2(02CtBu)41
two
in and
in
as
which
the
isomers
Mo2(02CCF elegant complex
02CCF5
review the
showed the
C2011.
the
showed
studies
=
analogues,
monodentate
is
prepared
with
of
several of
Na/Hg
NaOAc.
for
in
one
be
and
adduct
this
series
analogues,
fail
NMR
by
one-electron
reported
that
thf
not
molybdenum
1:2
same
samples
a
6”
examined
paramagnetic
"F
e
structure
preparation
system
that
supports
suitable was
their
the
barrier
concluded
in
could
reversible
generation
31P
solution
liagnds tungsten
is
W2(02CCF3)4
crystals
confirmed
Mo,(O~CCF,>~(O~CCM~>_ phosphine
it
(WC14jn
bonded
give
give
tungsten
the
of
of
than
with
which
of acetate
form
undergo
(2.542(2)2).
that
and
The
c2001.
reduction
quadruply
determination
studies
calculated
techniques.
twist
metathesis
methods
in
has
W2(02CtBu)4(PPh3)2
W2(02CtBu)4
isomer
a
positive
oxidative
thought
been
the
usual
carboxylates
long
present.
by
equatorially
one
potential
corresponding
adduct
less
near
core
the
in
corresponding
only
labile
by
the
with
the
following
The
axial
structure
with
at
isolated
with
in
at all). This conclusion -1 19,OOOcm to a forbidden 6'
isolated
have
reacts
of
contaminated
to
why
crystal
presence
was
the
reacts
are as
A
all
unimolecular
of 4-
present
prepared
tungsten
Iodine
phosphines
6
has
is
peak
considerably
Mo~(O~CCF~)~
it
allowed
be
shown
explains
system.
it
but
potentials
probably
and
effective
NaC02CtBul_
complex
was
the
been
but
It
(if
of
method,
-160°C_
and
CM~(O~CH)~~+_
being
partial
[1981.
performed
W2(02CCF3>4
for
[Mo2C1814-
low
becomes
presence
Neither
EMo2Br8]
distances for
Mo2(02CH)4
and
in
very
W2(0CtBu)4
by
between
been
that R
rotation
by
a is
internal
2_520(A(av)
electron
0,
of
method
assignment
transition
have bond
shown with
rotation
barrier
the
=
ligands by
B-MogBr4(dppe)2
characterized
MO-P
dppe
confirmed
(1991.
optical
the
was
consistent
orbitals The
was
calculations of
It
a to
reaction
Z-569(1),
metal-metal
alternatives
is
ligand
Prolonged
calculations
analogous
considered.
spectrum
to
yield
bridging
involves
which
Mo-Br
two
was
of
mechanism
trans-MoBr2(dppe)2 are
and
@Mo2Brq(dppe)2
isomerization
that ligand
chelated
of
The
proposed
within
two
structure
for MO-P
the
solid could
state)
~HL~,",Ymp;;
are
much with
in
be
> 31;
consistent
bond
more the
solid
99 state
[2021.
structure Reaction
of
Mo2(02CPh)4
CMo2(02CPh)4X212evolution
of
N 2 forming
of
was
2.879(1)x
adducts
and
2.1142
(X The
determined.
Two
derivatives
have
been
of
groups
while
the
C~S-MO
(OAc) (MeCN) 2 2 of 2.576(5)8.
bonds
are
In
axial
axial
in
attempt
ligation, and
W2(02CH)4 a s,s
ones,
it
may
ligation
Pyrrole
rationalize
is
almost
PPh4Br
in
with
= 2.121(3)x
CH2Br2
long
and
The
their
identical
in
gave
with
axial
C2031.
isolated
almost
this be
the
dtc
to
MO-Cl axial
crystal
both
cases
the
It
is
cause
of
at
(pdtc)
reacts
more
usual
of
multiple
aromaticty
of
the
characterization S2PEt3
with
=
MO-MO
the
with
of and
ligands
with
of
the
acid
3rd
the
have in
is long
W-W
MO-O
distance
adduct to
in
despite
performed
transition of
bond
itself,
the
behaviour
and
the
on
the
involvement
the
W-W
metals
tungsten
in
The
PPh30
structure
same
a
with
the paper
to
shown
(with
form
character ring.
The
The
2.77(2)%
axially
been
than
1st
towards
row
axial
other
C-N
structure
S2PEt3
ligand
is
give in
also
Pyrrole
dtc
linkage)
ligands,
would
reported
to
coordinates
C-N
dtc
linkage
similar
(88).
single
[Mo2(OAc>3(S2PEt3)(PEt30)l(BF4)
2.1384(8)2.
an
W2(02CEt)4
row
form
l,l-dithiolate bond
HBF4.
and
contribution
Mo2(0Ac)4 has
dithio
pyrrole
in
that
different
complex
the
C2061.
which in
that
other
of
C2051_
calculations
for
two
2.64(2)
that
considerable
lower
acetate
The
example
system
transpires a
the
chromium
as
two
of
triflate
observation
MO
makes
with
formation
Mo~(OAC)~,
distances 2_135R(av)_
bonded
same
in which
cis-CMo2(0Ac)2(MeCN)612+,
MO-N
the
the
orbital
coordinate
than
reported
one,
are
relativistic
c&-Mo2(OAc>2(pdtc)2(PPh30) appears
long
a quadruply
orbital
compared
been
In
distances
W2(02CH)4(CH3)2.
Since
have
MeCN_
to
Xor-SW
u-bonding
bonding.
and
or
expected
been
is
(0 SCF > which has axial 43 32 This compound is the first
W2(02CEt)4(CH2Ph)2
of
have
distance
as
MO-O
= Cl,Br)
very
MO-N
triflate
an
by
with
equatorial
coordinated
the
is
and
Mo~(OAC)~
replaced
MeCN
rather
it
2.128(l)
MO-MO
pyridine
[204].
groups
of
=
in
dissolves in CH2C12 (N3J212hcrystal structure of _ The
determined;
MO-MO
(~~H)~CMO~(OAC)~X~I
structures
(PPh4>N3
[Mo2(02CPh)
CMo2(02CPh)4C123
(PPh4>2cMo2(02CPh)4C121 bonds
with
compounds.
because
lead the
to
preparation
from
the
that
described
reaction
in
the
dithio
PEt3
to
give
(89).
The
loss
of above
acid
form
f2071. Mo2(mhp)4
reacts
with
cfs-Mo2(mhp)2C12(PEt3)2 shows
strong
fluorescence
which
fluorescence lifetime
SiClMe
even of
33.8ns
3
has in
in the
the
structure
ordinary
[208].
presence
of shown
laboratory
in
illumination
compound and
has
a
100 Me
I
o’co ’ MO
/
5’L I
Bond
distances
c
O\PPtl
AS’
3
h14
(88)
are
MO-MO MO-O(OAc)
=
2.134(l)
=
2.115(7)
=
2.444(3)
=
2.370(7)x
MO-S Mo-O(ax)
Me
PEt3 Bond
distances
are
MO-MO
e
2.103(l)
MO-O
= 2.052(6)
MO-Cl
=
2.435(av)
MO-P
=
2_559g(av)
101
Mo2(R-1,2-pn)4 been of
recorded.
has After
bridged
A made
the
techniques.
Huckel
treatment
bonding The
is
the
A
based
on
been
8
CD
spectra
have
(bridged)
that
the
Boltzmann iodo
the
and
hexameric
isomers
only
the
familiar
been
triplet
influence
prepared
by
on
of The
lifetime
analyzed
in
levels
been
W6114
the
c2101.
energy
have
W6112,
extended
strong
smalL
1.4-3OOK.
has
been
from
a
be
has
resulting
lifetime
clusters
been
clusters
more
have to
range
this
include
has
the
orbital8
luminescence
populated
They WI 3
than of
appears
over
increases
[M6X814+
d-electrons
anomalies
with
ternary
The
cZuster
new
been
prepared
They
all
~~-0
groups
and
and
(two
to
connectivity
refluxing
an
isoelectronic
particular
terms
W6117
and which
interaction
of
[2111.
prepared
and
series been
of
of
Chevral
reviewed.
temperatures, potentials
interactions
their are
all
the
the
of
influence
the
the
All value
ions,
phases show
of
electrical
which
indicating
stability
of
the
that high
C2131.
species
LiZn2M0308
characterized the
Mo3013
three
0x0
one
other
formula
have
ionization
phase
compounds
contain
clusters
of
at
second
rhombohedral
Other
The
the
metal-sulphur
temperature
cluster
properties
= Ca,Sr,Ba,Yb,Eu,Sn,Pb)
structural
(90)
that
of
in
rather
d band
overlap
determined
determined. 4+ cW,I8) core.
(M-
correlate
in
and
concluded
bonding
the
and
orbital
tungsten
physical
M,II Mo6S8
2.7.4
was
and
C2121,
The
the
narrow d
several
of
the
(chelated)
it
physics that
constants
elements
and
metal
temperature
for
number
absorptLon
c2091.
dependence
the
emissions
lattice
too
3 has
as
a
the
metal-metal
emerges
though
temperature
(NEt4)2CMo6C114
the
of
It
even
decreases
exists
of
methods
Huckel
the
with
its
species
re-examination
using
and
Mo2Cl4(S,S-dppb)2
isomer
Hexameric
2.7.3
prepared
comparison and
Mo2C14(R-dppp)2
staggered
been
Zn3M0308
IR,
magnetic
cluster ligands
MO 0 0 3 4
by
(I),
containing on
cluster 6/2'3/3-
each
and (I)
(II) and
and
to
two
(II)
ScZnMo
0 38 diffraction
X-ray
within
molybdenum
one
and
each
unit
which other
have
bridge
clusters) one
unpaired
( III)
have
studies.
one
~~-0,
three
to
other
to
give
a
electron
per
[2141_ black a
crystalline
toluene
C2151.
solution
compound
Mo4(u3-S)4(p-S2CNEt2>(S2CNEt2)4
of
for
Mo2(S2CNEt2)6
2Ohrs.
Its
was structure
made is
by
shown
102
Mo2
S
-
‘C -
NR2
S
S (90)
C
R N" 2
Bond
distances
are
Mel-MO2 MO-US Mo-S(u-dtc)
Reaction
2.732
(5)
=
2.32(
1)-2.40(l)
=
2.51(l), 2.56(1)x
of
compound
could
and
has
oxidatively
the
compound
through
their
showed
it
molybdenum
Li2[Fe2S2(C0)6]
expected
and to
atoms
consist and
a of
two
with
=
-78OC
shown
in
(P-XC~H~S)~
structural
1)-2.54(l)
2.48(
at
structure
decarbonylated
(NEt4)4CMo2Fe6S-,2(S-P-C6H4X)6
bromide
(92)
be
which
MO-MO = 2.861 (6)Cav) MO-S
(NEt4)2[C12FeMoS4]
(NEt4)2[MoFe3S6(C0)61
give
other
=
(X
gave @1)_
= Cl,Br)
determination
two MoS4(Fe-SRI3 3 persulphide
on
cubanes groups
u2-q
The to
the
linked as
shown
in
C2161. MS-Xa
calculations 3_ The [MoFe S (SH) ] 34 6 The clusters. MoFe3S4 reported
previously
have geometry results
for
the
been
carried
selected of Fe4S4
the
out was
on
that
calculations
clusters
C2171.
the found were
hypothetical in
the
compared
cluster single wFth
cubane those
103
Average
bond
distances
are
MO-Fe
=
2.762
Mo=S
MO-uS
=
2.263
Fe-pS
=
2.156
= 2.262x
(92)
Bond
distances
It
has
are
been
multi-electron was
shown
Mol-s8
=
2.47(4)
Mel-S9
=
2.40(l)
Mol-S18
=
2.64(5)
S8-S9
=
l-99(5$?
found
that
(NBu4>3[Mo2Fe6S8(SPh)91
electrochemLcal that
it
is
the
reduction
reduced
form
of of
in
RN3
the
to
MeOH/thf
give
cluster
NH3,
which
catalyzes N2H4
reacts
the
and
RNH2.
with
RN
It
3
C2181. The bridging
double between
corresponding to
The
atoms
iron.
changed
one-electron phenoxide
MO
[MoFe3S4(SEt2>3]2(p-SEt)3
phenoxide
coordinated markedly
cubane
by
is
more
each
S 34 magnetic
The the
reductions
molybdenum
in [MoFe
cluster)
difficult environment
to
reacts
(OPh)
1
substitution. similar
(which
to
The those
reduce in
the
the
with with the
compound of
has PhOH the
double shows
parent
three to
SEt
yield
groups the
phenoxides cluster two
are
not
quasi-reversible
compound,
although
the
12191. MO/Fe/S
cluster
in
nitrogenase
has
been
104
examined
by
structure and
comparison
(collectively
a
variety
of
results
show
the
and
of
to
those
coordination
Two
EXAFS
cubane This
nitrogenase
in
result
one-electron for
the
of
and
MO/Fe/S
the
type
information
reversible cofactor
of
two
absorption natural
MoFe3S4
are
clusters
complements
edge
of
quite
is
near
MO/Fe
known
cofactors
to
the
consistent
edge
structures_
similar
containing
and
and
isolated
complexes
nitrogenases
each
The other
MoS
with
0 33 the
[220]_ reductions
molybdenum-iron
N-methylformamide
X-ray
XANES)
MO/S
XANES
the
MO-K-edge
called
synthetic MO
unit_
independent
MO/Fe/S
of
the
have protein
been of
observed
Asotobao*er
for
isolated
vine&n&i
[2211_
ACKNOWLEDGEMENTS
I
thank
reading
the
Penny
Panagiotidou
and
Katherine
McGregor
for
carefully
proof
manuscript.
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168, 169, 170.
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(1985) 182. 183. 184.
8276
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241
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4565 185.
T.W.
1643
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109 186.
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Chisholm, Smith and Chisholm, Cotton and Chisholm, Ahmed,
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M.H.
Chisholm,
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24
(1985) 4039 191. M-H.
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2.
AND
MX.XBDENun
29
TUNGSTEN+
R. COLTON
CONTENTS
Introduction . . . . . . . . . . . . . . . . . . * . . . . . . . ...* . . . . . * . Molybdenun(V1) and Tungsten(V1) .......... 2.1 . . . . . Halides and halo complexes ......... 2.1.1 . . . . 2.1.2 Oxides, rolybdates and tungstates ..... . . . . Monomeric 0x0 complexes .......... 2.1.3 . . . . 2.1.4 Dimeric and polyaeric 0x0 complexes .... Coaplexes with oxygen donor ligands .... 2.1.5 sulphur donor 2.1.6 Thioaolybdates, thiotungstates and complexes .................. . . . . . . . Homonuclear polyanions ........... . . . 2.1.7 . . . . . . . 2.1.8 Heteronuclear polyanions .......... Coaplexes with nitrogen and phosphorus donor 1 igands 2.1.9 . . . . Molybdenum(V) and Tungsten(V) ........... 2.2 2.2.1 Halides and halo coaplexes ......... . . . . Monomeric 0x0 complexes .......... . . . . 2.2.2 . . . . 2.2.3 U-oxo, Lr-sulphido complexes ........ Complexes with nitrogen donor ligands ... . . . . 2.2.4 . . . . Molybdenur(IV) and Tungsten(IV) .......... 2.3 2.3.1 Halides and halo coaplexes ......... . . . Complexes with oxygen donor ligands .... . . . . 2.3.2 . . . . 2.3.3 Coaplexea with sulphur donor ligands .... 2.3.4 Complexes with nitrogen and phosphorus donor 1 igands 2.3.5 Complexes with metal-carbon bonds ..... . . . . . . . . 2.4 Molybdenun(III) and Tungsten(II1) ......... Molybdenum(I1) and Tungsten(II) .......... . . . . 2.5 2.6 Molybdenum(O) and Tungsten(O) ........... Metal-aetal Bonded Species . . . . . . . . ._~~. .. . ._ . . . . . _~~~. . . 2.7 Triple bonded species of molybdenua(III1 and tungsten (III) 2.7.1 2.7.2 Quadruple bonded species of molybdenur(I1) and tungsten(II) 2.7.3 Hexwric species . . . . . . . . . . . . . . . . . . . . 2.7.4 Other cluster species . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . l
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29 30 30 35 37 46 49 51 54 55 57 62 62 65 66 70 72 72 73 76 78 80 82 87 88 89 89 97 101 101 104 104
INTRODIJCTION The inorganic
review and
on molybdenum coordination
Chemical
Abstracts,
1985
some
and
Organometallic included
in the
chemistry, review,
tungsten
chemistry
Volumes
published
and
102
towards
and
103.
the
end
including but
of
reference
chemistry
the
elements
Thus of
this
most
1984
carbonyl is made
which of
will
+ HO REF'llINT8 AVAILABLE
0010~8546/S8/$28.35
@198SElsevier
SciencePubliahersB.V.
deals
with
was
cited
in
the work
published
be reviewed.
chemistry, to some
year
is not papers
formally
of general
the
in
30
interest. The year_
arrangement
The
oxidation
state
determined
by
are
of
2.1
MOLYBDENUM(V1)
2.1.1
HaZides
of
donor the
apply
to
both
AND
ha20
fields
M02F2
was
good
the
gas
The
measurements
(M
and
at
mean
= Cr,Mo,W). WF6
reacts
and
rate
of
were
MOF4
(MO).
Ba2CM02/2 units_ IR
0
have
of
1
2-
were
B4
being
which
are
separated almost c73.
mono-
a
and
the
been
reaction
with
IR,
the
the
ordering the
M
been
is
is
compounds
used
where
calculated
and
for
experimental
MF6 data
-, NO -, SF - and SF - in 2 5 3 6 ratios have been determined. of
WE6
is
mass
volatility
difficult
single
BC13
small of to
After
x
lo4
and
as
showed
single
the
tungsten(VI)
peroxo
in
and
The
formation
l-96
+
19F
034
SF02
Compounds
NMR
The
studies
crystals
(W)
to the
[41. or
a
anion
containing All
the
H202
and
tungsten
species
constants 3-52
as
be linked
predominant
x 1012<
[31_
C14Mo=NTeF5_
of
and
F4M=NTeF5
solutions
the
MF6
reaction
electrode.
and
of SiF4
compounds
chains
selective group
the
gave
spectral
derivatives.
7.15
extraction
insoluble.
by
by
of
+ H2NTeF5
prepared
fluoride
interaction
prepared
2Me3SiF
been
a
trifluoro
chlorination
by
NO
affinity
by
is
studies
using
104(01<
negligibly
The
I-,
-
by have
formation
studied
x
have
branching
obtained
have
+ MF6
compounds
complex
4.84
symbol
calculated
electron
method
group
compound,
contained
the
ranges
the
Crystallographic
been
complexes
Br-,
and the
vibration
F IF with the structure containing 2 2 2 and Raman spectra were reported [51.
Fluoro F-
the
complexes
The
last is
tungsten.
between
Cl-,
are
characterized
Ba2[M03F4] powder
F-,
that
pure
CNTeF5
molybdenum
compounds
of
agreement
with
advantage
the
the
and
for
material
state
ligand
type.
review
of
TUNGSTENtVI)
coefficients
2Me3SiN(H)TeF5
With
the
121.
The
containing
mixed
molybdenum
of
oxidation
ligand
amplitudes
indicated
yields
120°C.
With
that
presentation
each
dominant
The
El].
3.3(+0_04,-0.2)eV
within
atom.
to
the
comptexes
phase
High
and
of
similar
ordering
metals
type
and
and
the
is
of
terms
in
comments
Force
material
criterion
the
described
similar
of
primary
observed
lie
in
with
x 1O1'
the B2
and
[61_ W03
and
separate. with
Et20
filtration,
tungstates
gives
It
been
has
since
now WOC14
evaporation
is
mixtures found very of
the
of
that
WOC14
they
soluble solvent
and
can
and
W02C12
be
easily
W02C12
gave
pure
is WOC14
31 Interaction solution
gave
crystals
of
structure
of either
a mixture
the
of
latter
MoC15
complex
the anion
or MoCI4
of MoC13(N3S2) were
is shown
in
with
and
(NSC1>3
in dichloromethane
CN(SC~)~ICMOCI~(NSC~>~.
characterized
by X-ray
Black
diffraction
and
the
(1).
S-Cl
i’,N
~1,
/ (1)
MO
I’
’
Cl
Cl
Cl
Bond
distances
are
MO-N
= 1.75
N)
= 2.47
MO-Cl
N-S
= 1.59
S-Cl
MO-Cl(trans
The
MO-N-S WClS
dimeric
unit and
with
(PPh4)CW2NCl10
is linear
(Me3Sij3N chloro
bridges.
1 which
I
and
react
was
Cl,
the bond to give However,
shown
/Cl
Cl
N--/W\ Cl
double
on
the basis
with
(PPh4)C1
diffraction
Cl,
Cl
suggested
which
on reactton
by X-ray
A"\
Cl
lengths W2NC19
= 2.32-2.37 = 2.038
to have
bonding of
(81.
IR data
is
it gives
the
structure
-
,Cl
c1 Cl I
(2)
(R)_
32 Bond
distances
are
W=N z 1.79(Z),
N)
=
2_367(6),
N)
=
2.276(6)-Z-316(6)8
w-cl(tnzns w-cl(cis
The
W-N-W
unit
solution
of
is
linear
and
(PPh4)[W2NCl101
the in
(PPh4>2[W3N2C1141_CH2C12_CC14
remarkable
CH2C12 by
are
almost
structure
linear
corresponding eclipsed
but
to
of
the
configuration
I
and
double
slowly
CC14
forms
bonding
[9].
crystals
A
of
reaction
[W3N2CL14]2-
anion
in
asymmetric double
suggest
this
compound
nitrido
bonds.
+ WC16
is
bridges
The
shown
with
equatorial
WC14
in
W-N
(3)_
bond
units
There
lengths are
in
the
[lo].
Cl,
Cl
and
lengths
-
the
highly
single
2.399(6)
bond
2[W2NCL101-
The
l-88(2)
/Cl
Cl,
,W\
N
Cl,
N
,W\
Cl
Cl
,,I
Cl
Cl
2-
/Cl
C1
,W,
Cl
Cl
(3)
Average
bond
distances
W=N W-Cl(trans
The
of
isolated W-N-C linkage
as unit
NEt3
its is
[ll].
= 1.835
N)
interaction
quantities
are
= 2.40
of led
(AsPh4)'
almost
and
WC13N to
the
(CF
formation
salt.
linear
W-N
=
2-065
N)
=
2-312
W-Cl(c$s
and
The
) CO 32 of
in
structure
there
may
MeCN
C(WC15j2 of be
the
triple
in
the
presence
anion bond
is
of
12-
p-NC(CF3>2N
shown
character
catalytic
which in
(4).
in
the
was The W-N
33
2-
l,i’,
1 C
C
Cl
/;1
(4)
c1
Cl
Bond
distances
W-Cl(trans
Two
groups
groups
the
Both
structure is shown double
[12,13]
have
[MC13(N3S2)12
and
ligand.
= 1.743(15)
in
to IR data,
tungsten
the
reported
are made
compounds
of
C-N w-cl(&a
N) = z-437(7)
According
(NSCl13.
CF3
are
W=N
complexes
A
CF3
tungsten
WN3S2
dark
compound unit
(AsPh4)Cl was
cyclothiazen,
through to give
determined
is planar
of MoNC13
compound
is associated
with
brown
interactions
the molybdenum
complex react
that
by the
= 1.415(22)
N) = 2.304(9)-2,326(8)2
and
is bridged
the Y-nitrogens
cl21
the W-N
by X-ray distances
Cl
s/
N,l,cl
N
\
(5)
S-N/!\
I
Cl Cl
I-
Bond
distances
are
W-N W-Cl(trcms
N)
= 1.85tav) = 2.44
W-Cl(cis
N-S
= 1.54-l-61
N)
= 2,398(av)
with
by chloro
(AsPh4)[MC14(N3S2)l
bonds.
r-
[N3S2]-,
and WCC14
of
the and
diffraction correspond
the and to
34 Reaction crystals
between
of
(AsPh4)[WClq(N3S2)1
(AsPh4[WOC1_,(0S2N2)] determination The
WNSNSO
(AsPh4)[C14W
ring
the is
could
latter
planar
Bu]
and
described
which
on
C
be
the
above
separated
compound and
S4N4
bond
and by
revealed W-N
in
the length
dichloromethane red
hand
crystals
brown
of
picking_
A
stereochemistry corresponds
gave
structure shown
to
in
a double
bond
c143.
Cl
O\\l/
c/j\
(6)
Cl
Bond
distances
are
W-N
=
l-833(4)
w-0
=
l-699(3)
N)
=
2.406(l)
W-cl(trans
Mo02C12
reacts
with
(7)
=
2-288(3)
N)
=
2.381(1)2
diisopropyL~N,N-diethylcarbamyl)methylenephosphate, to
(iPrO)2P(0)CH2C(O)NEt2,
w-cl(cis
w-o
give
the
1:l
adduct
whose
structure
c151.
Cl
,/i’\ \
(7)
Cl
LPrO
-
/“ OiPr
’
I"
yCANEt2
is
shown
(6).
in
Average
bond
distances
are
Ma=0
=
1.682
MO-Cl
=
2-3802
MO-O
N,N-dichlorophenylsulphonamide give
polymeric
monomeric
=
reacts
[(PhS02N)2WC12]
which
x
the
(PhS02N)2WC12(MeCN)2
on
2.233
with
W(CO>6
in
dissolution
structure
of
in
which
refluxing
MeCN
is
gave
shown
CC14
to
crystals
in
(8)
of
[161.
0
\“/
MeCN
\
/“\
MeCN
H-0 H
N-S
Ph
(8) Ph
/
N-S
\x 0
Cl
Average
bond
distances
are
W-Ncnitrene) W-Cl
The
W-N(nitrene)
The by
standard
solution
of
laser
Raman
W30g
and
=
2.3352
= 2.226
surprisingly
long.
and tungstates
to
be
cl?'].
W4012
spectrum
W-N(MeCN)
is
with
of
W03
of
Moo3
of
W03_2H20
-(1430.1+1.0) The
technique
W206 has
and
sublimation
with
been
mass and
and
W308
have
been
determined
-(1133.0*1.0)kJmol-1
of
W03
spectral
reported
W03.H20
has
been
analysis.
present and
as
minor
assigned
investigated
The
vapour
species on
the
by consists
[18].
basis
of
The C3v
C19J.
Co-condensation and
1.775
enthalpies
298.15K
effusion
mainly
symmetry
molar
at
Knudsen
=
distance
calorimetry
respectively the
bond
Oxides, mob~.b&tes
2.1.2
o
photolysis
of
the
slurry
vapour
with
of
condensate
the
MeOH
at in
-196OC MeOH
gives under
Mo205(0Me)2.2MeOH 02
gave
(Me012CH2
36 in a slow new
catalytic
form
It has biochemical bound
been
Manganese
products
depending
different
the hydrates
diffraction (9)
and
with
water
H20
gave
a
be a viable of
probe and
[M004]~-
for
[MoS412-
by precipitation
the
At pH
solution.
the
from
into
other
7-8
of tetrahedral
tetrahedra
share
aqueous more
the product molybdate
corners
obtained
and
with
four
to manganese.
At higher
been
by annealing
coordinated
solution.
crystalline
temperatures
to a-MnMoO 4 c221.
(W:Na:Li
revealed
slight
may
spectra
at 60-100°C
of Na6LL2[W20101
Lip0
NMR
consists
in which
transform
study
prepared
transformed
the pH of
with
spectroscopy
the 95Mo
its structure
crystals
of wo 3, Nap0
of MOO., with
[211_
were
was
units
octahedra
Single
in
albumin
upon
and
co-condensation
MO NMR
by examining
serum
Mn(I1)
95
that
molybdates
MnMoO 4.H20
all
shown
precipitate
octahedral
Similar
[20].
systems
to bovine
The yellow
was
conversion.
of Mo03_2H20
have
= 1:3:1)
mixtures
at 840°C for 60 days. An X-ray 8anions with the structure
[W2010]
discrete
asymmetry
prepared
in the 0x0
bridges
shown
[23].
o\i,“\i/o 0
+lo/+o
6 )
0
0
Bond
distances
are
w=O
The
correlation
between
phosphate
tungsten
estimates
intermediate
physical
bronzes
measurements
A new
which
The
structural
columns
of
Relationships
the ReO 3 type
Potassium to prepare
and
brown
groups.
length
has
valence
6 for
the valences.
d-electron tungsten
framework
the mono
by
has
mixed
indicate
been
valence
2-1642
5 and
extending
bronzes
and
= 2.024,
other
diphosphate
with
vapour
tungsten
bond
between
reddish
synthesized.
W-MO
I 1.809-1.916
can
along bronzes
directly
this method.
applied
oxFdes
This
with
Attack
on
and
has
as 2 x 2 W06 connected
are discussed W03
led to with
[241.
CS[P~WSO~~]
COO11
to
is in accord
delocalization
be described
phosphate
reacted
tungsten
bronze
indefinitely
been
crystals
the oxide
been octahedral by P207 C251,
in an attempt was
extensive,
37 but
only
limited
(200-900°C The
for
compound O-25-168h)
interaction
following
in
observed
under
the
conditions
employed
R3SiOH
(R
=
Ph,'Bu)
with
the
2-
[Mo2071
ion
gave
the
reaction
structural
as
was
1261.
of
2R3si0~
A
formation
-
Z(NBU~)CR~SIOMOO~I
+ H~O
\ IPhPh
study
(10)
(NBU~I~CMO~O~~
+
of
(271.
the
salt
with
R
=
Ph
confirmed
the
structure
of
the
anion
Si-0
-
/
Ph
Bond
distances
are
Mo=O
2-
also
cMo2C71
in
2.1.3
Monomeric
has
(10).
appeared
monomeric, reactions a
different
a
It
and are
seven
is
very
MO&
=
MeCN
was
structure
1.884(4)x
to
give
followed of
similar 2.154(6),
of
coordinate all
0x0
the
progressively by
visible
final
to that MO-~0
at
between group
to lower
be pHls
tungstate 1
using
cryoscopic
and H
complexes.
dimeric
and
of =
absorption,
product its
analogue
l-881(7)2
C28l.
NMR
in of
molybdenum
the
metal
chemistry
and
includes
the
Mo(VI).
and and At
species
thiomalic l3 C
states of
tungstate
0x0
structures
oxidation
complexes
between
polarimetric,
thought
but
sequence The
cover%
number
by are
reaction
of
formation
investigated observed
in
(Me3Sij2S
=
0x0 comptexea
review
of
Complex
with
distances
C293_
structures
MO-PO
determined
Bond
general
1.699Cav)
spectroscopies_ was
shown
A
reacts The
[MOO 3_xSx(OSiMe3)l-. 17 95 MO and 0 NMR [MoS3(OSiMe3)]-
=
acid
Z(-)malic acid 1 H NMR methods. high
pH
(>7)
predominate at
spectroscopies.
pH
has All the
[30], 2-7 A
been
have number
the
stable
species complex
is
Similar been of
conducted 0x0
by
38 complexes
containing
Reaction
of
two
thiomalate
Mo02(acac)2
ligands
with
a
were
series
of
identified
[31].
2a-hydroxybenzimidazoles
(L)
(11)
Y
(11)
gave H
Mo02L2.
and
the
Z
A
= Ph
alkoxy
crystal
showed
structure the
imino nitrogens trans 95 MO NMR spectra were previously
ligand
The
oxygen.
and
two
to
to
the
&s
recorded
oxygen
for
donor
oxygen
two
ccs
and
0x0
2.059(4), trans
one
atoms
to
0x0
the
different
=
Bond
group.
compounds
appropriate
by
reaction
The
sterically LN(OHj2 with
respectively. (13).
2R2NOH
(R
(mixed
with
separation
complexes
and
its 2
183W
structures
dmso of
case
= Et,bz)
-
IR
both
two
In
this
=
trans
the
case to
1.938(S) in
force
prepared
from
in
+
W02(R2N0)2
the
and each
case
the
the
W02C12
by
spectra
very
shifts
of
the NEt3
2(Et3NH)C1
were
chromatography similar
were
and
presence
complexes
achieved
to
prepared and
those
recorded
of
their
[343.
-diphenyl-2-hydroxyethyl)-
LN(SH)2
have
Mo02(LN02)(dmso)
compounds
within
The
[331_ were
2,6-bis(2,2'
give
the
given.
fall
distances
effects
monooxomonothio)
analogue to
steric
and
with
are
MO-O
longer
=
with
Mo02L2
dichloromethane
chemical
ligands
sulphur in
this
in
1.70(av), the
that
was
gave
their
demandtng and
Mo02(acac) The
2NEt3
=
they
Mo(VI)
Y
with
not
structure.
ligands
with
in
+
and
analogues
pyridine,
and
+
B2S3
recrystallization.
(12)
in
different
Mo=O
suggested
arrangement
dithio
with
molybdenum
reacted
was
N,N-dialkylhydroxylamine
corresponding
The
It
are
2.325(5>%
c~s-WO~(R~NO)~
W02C12
The
and
a
= H,
nitrogen
were
studies
X
octahedral
and of
with
imino
is
complexes
Similar
different
the
distances
complexes
[32].
distances
2.142(5)
structural
The
from
Bond
the
dioxo
revealed
nitrogen
groups.
MO-N
all
compound
molybdenum
groups.
C&Y
the
through
about
for
range
on
chelating
0x0
2-o-hydroxyphenylbenzimidazoles one
be
stereochemistry
established
nitrogen
determination
were
been and
determined
prepared
and
Mo02(LNS2) and
are
shown
in
39
Ph \
0SMe2
/\ Ph
Ph
Ph
Ph
\/
(13)
Ph
Ph
Bond
distances
are
Mo02(LNOp)(dmso) MO=*
1.705(4)
Ma-0
1.902(3)
l-694(6)
MO-S
The
2.415(2)
MO-N
2_417(4)
MO-O(dmso)
2.382(7)R
bond
Mo02(LNS2)
to dmeo
in Mo02(LN02)(dmso)
2.244(7)
is long,
implying
lability.
MOO~(I.NS~)
is
the
first
five
coordinate
trigonal
bipyramidal,
reported
[351_
The
complexes
molybdoenzymes 0x0
system
Mo02(LNS2)
to and
which
turns
and
Mo02(LNS2) from
over
the
Schiff
base
MoO(LNS2)
reacts
coordinating ligands
AA
thought
to be
compounds
(AA
have
salicylaldehyde A
where
and
is the
-
(14)derived
to form This
compounds
models
to yield
coupled
for
are
0x0
MoO(LNS2)
to produce
Me2S
+ PPh30
from
salicylaldehyde
reported
Mo02(sal-shz)(H20) compound
en etc)
blpy,
coordinate
on
to give
containing
transfer
and
and
with
with
the
ligand
bidentate
nitrogen
MOO of
(Sal-shz)(AA) which 2 IR studies [371. Very
the Schiff
base
derived
are similar
from
Schiff
Mo02(sap)(im1d) base
have
been
synthesized
(15).
(15) C=N H
compounds
Mo02(sap)(EtOH)
were
prepared
followed
PPh30.
a catalytic
OH
The
also
C381.
complexes
tridentate
reacts
the basis
benzoylhydrazide
of octahedral
series
H2sap
been
useful
PPh3
been
is approximately
H
O-&O_
= phen, seven
geometry of both
are
with
have
+ PPh3
(Sal-shz)
is known
through
the
reaction
H
SalFcylhydrazide
and
properties
substrates
Me2SO
The
complex
Electrochemical
[361.
transfers
Mo(V1)
/
from
Mo02(acacj2
by reaction
with
and H2sap
imidazole
in EtOH
[3gl.
to give
41 It has reduction rapidly
been
shown
of N02gives and
reduction
of MoO2(dtc)2
N20
reports
both
MoO2(Et2dtc)2
by HCOOH
Mo02(dtc)2
MoO(dtcj2
Two
that
to N20
and
The
respectively. by HCOOH
have
Both
[N,O,]-.
appeared
and
The
in dmf,
rate
MoO(Et2dtc)2
reaction
products
react
determining
catalyze
of MoO(dtcj2 with
step
HCOOH
in the
the
with
N02-
to give
is
cycle
the
[403_
on
the preparation
2,3,8,9-dibenzo-1,4,7,lO_tetrathiadacane
of MoO2cdttd)
where
dttdH2
is
(16).
(16)
Reaction [411
of Mo02(acac)2
while
reaction
Mo02(dttd) the
pure
and
the
complex.
structure
in thf
dttdH2
Mo203(dttd)2
Mo(VI)
revealed
with
of dttdH2
with [42].
in
temperature
diffraction (17) with
in MeOH
oxidation
However,
An X-ray shown
at room
(NB~,>,[M080263
of
study
the
this
on poor
thiolates
gave
gave
Mo02(dttd)
a mixture
mixture
yielded
quality
trana
of
crystals
to one
another
\9 s\i./o ’
(s/j”\o
(17)
s
b b
(MO-S with
much
complex scale, and
and
= 2.402(7)g(av)) longer
shows but
on
the product
species
MO-S
MoO(dttd)Cl.
of
time
CMoO(dttd)CllThe
&rans
2.687(6)x
one-electron
coulometric
was
thioethers
distances
a reversible the
the
to each
C423.
reduction
In the on
a two-electron
which
could
&S
0x0
presence
reduction
be oxidized
properties
the
of
to the
these
and
groups
of NH4Cl
the voltamnetric
scale
electrochemical
of
the
time
was
observed
EPR
active
related
42
complexes site
were
of
the
described
molybdenum
CataLytic MoO~(L-L)~ alkyl
and
air
or
cofactor oxidation
Mo~O~(L-L)~
ester,
related
of
the
of
benzil
in
(L-L
cysteine-n-
catalyst
the
behaviour
of
the
molybdenum
binding
[423.
complexes
S-deprotonated
deactivation
to
dmf =
occurs
Et2dtc,
decylamide)
occurred
due
to
in
the
presence
S-deprotonated but
in
formation
of cysteine
most
cases 2+ [Mo2043
of
a
slow
species
c431. Compounds
of
the
1-dithiocarboxylic
type
acids
MoO~(L-R)~ (18)
were
(w h ere
L-R
prepared
by
=
2-(alkylamino)cyclopent-ene-
reacting
I-IL-R with
Mo02(acac)2.
R
C-3)
\ /
H I I
;_
I
/ HS
Mo02(L-RI2 to
complexes
coordinate
coordinate. examples
With of
Mo(IV)
very
has
Moo3
rare
to
give
atoms,
reduction
MoOCL~(L-R)~. so
the
occurs
paramagnetic
(u
to
=
The
chloro give
ligand
is
derivatives
Mo(L-R)~
2.35-2.77BM)
which
eight
thought
are
seven
are
coordinate
shown
heating,
prepared
to
be
it
loses
by
the
of
water
Mo02(02).H20
on
a mole
action the
of
basis and
H202 of
half
on
IR,
the
UV
a mole
metal
and of
or
on
thermal
O2
to
give
[451. and
Moo3 excess
thf
crystals the
HCl
peroxide',
been On
HCl
sulphur
c441.
'Molybdenum
studies,
with
both
excess
the
systems
MoO3,
react
through
thf
were
exposed
to
of
of by
pentagonal bonded
any
X-ray
strong
bipyramidal
After
crystallized
addition in
and
light.
77K
and
Addition
the out
oxidizing
diffraction
which of
malonic
presence at
pH
is
of
of
3.
Malic
acid
for to
a
H202, also
resulting
water
and
Fn
peroxo
colourless the gave
of
complex the
The
groups
structure to
peroxo
be
in
in was
a
groups
are
linkages_
solution
of
Moo3
in
K2CMo0(02)2(ox)j oxalato
with
gave
peroxo
the
atom
[46].
stirred
18-crown-6
but
molybdenum (19)
Mo(VI)
solid
formation
surprising, the
shown
usual acid
is
showed as
excess
the
The agent
which
environment
asymmetrically,
solution
air
at
[MoO(02)2(H20)2](18-crown-6)_H20_
absence
confirmed
co-condensed
complex
KOH
gradually and
the
43
Bond
distances
are
MO-O Mo-H2O(ax)
mechanism
of
confirmed
the
before is
but
the
to
donor
structure and
The
of
data
for
new (19)
not
the
the
The
compounds
X-ray
the
diffraction
structure
has
accurate.
The
structure
replacing
the
aquo
groups
with are
the
again
given
0x0
and
slightly has
1_716(7)
one
M-0(02)
1.940(1),1.960(l)
1.935(6>,1.966(6>(av)
M-O(ax)
2.269(l)
Z-245(6)
M-O(eq)
2.051(l)
2.033(6)x
K2[MoO(02>2(C6H607>]_l/2H202_3H20
the
group
of
and
the
interesting
anion
feature
citric
is
has
acid
shown
in
the
in (20)
the
the
anion
so
the
carboxylate [471_
determined
The C481
below.
1.676(l)
K2[Mo04]
of
ligands,
been
M=O
of
determined
asymmetric
also
K2[WO(02)2(ox)l
complex
study been
more
K2[WO(02>,(ox)~ are
1_920(4)
group
bipyramidal
peroxo
An
complex;
is
isostructural
both
the
oxalato
pentagonal
1_900(4),
= 2.084%
understood_
of
determination
axial.
=
K2[Mo0(02)2(ox)1
interaction
is
been
isolated
presence
of
similar
coordination
of
to the
from
excess
the
the
H202_
oxalato
deprotonated
The
complexes hydroxy
C491. The
proline
interaction etc)
in
of
the
MoO(O~)~(HAA>(H~O). derivatives discussed the
MO-O(02) Mo(H20)(eq)
is
with
is
stereochemistry but
2.325
reaction
stereochemistry oxygen
l-647(4)
=
identification
this
similar
=
form
above. their
presence Crystal
revealed
of
Moo3
very
The
amino
Zwitterions
and of
amino H202
structure similar acids as
acids gave
shown
(=
complexes
in
on
which
coordinated (21)
glycine, of
determinations
structures are
HAA
are in
for
the the
or-alanine, type glycine
closely
a monodentate the
valine,
glycine
and
related fashion complex.
proline to
those in
0
“7Jl/”
1. I / / OI"+O
C02H
’
0'
0
CH
2
.C
\C
YC C02H
Bond
distances
H2
II
0
are Mo=O
Mo-O(ax)
=
l-655(8)
MO-0(02)
= l-926(9),
=
2.220(8)
Mo-O(eq)
=
l-975(8)
2.011(7)%
H II
H \I/ N
0
\
0
C4
2I
\
II/O\
0 \
0
M*
o-
\/
(21)
0 OH2
Bond
distances
are
Mo=O MO-0(H20)
=
1,680(l)
=
2.346(1)2
MO-O(O2)
=
1.932(1)-1.962(l)
45 The
peroxo
above
groups
the
are
pentagonal
only
~is-[Mo02(pip-N0)21 its
substituted
in solution methods.
showed
reacts
their
and
in
to give
been
confi.rmed
to be
with by
atom
is 0,362
the
(catechol,
chelated
a structural
in a pentagonal
H2cat)
and
compounds_ They are rigid 1 H and 13C NMR using
investigated
symmetry
Cs
atom
the molybdenum
[SO].
MoO(pip-NO)2(cat)
have
this
was
and
group
1,2-dihydroxybenzene
inferred
the molybdenum
shown
the 0x0
with
structures
results
plane
asynxsetric
towards
derivatives
and
The
the mirror
slightly
plane
catechol
lying
determination
bipyramidal
in
which
environment
as
(22).
0
II/O\ I\
CT
-N
;\MO
N’
G \ 0 0
0
Bond
distances
I
are
Mo-O(cat)
MO-O = 1.688(6) MO-O
The
Mo-O(cat)
trans
bond
to the A
0x0
series
NCS,NCO,N3)
of
have
distances
group
are
the
types
observed complexes an inverse chemicals
g5MO
NMR
of
the
prepared
spectra
[MoL(dtc)3]"+
of
a range
halogen shifts
type
C521
of
+ 2XX
is no
apparent
lengthening
180ppm
to
WO(OR)2X2
seven
+ 2KCl
coordinate X = Cl,Br)
complexes have
1+ and MoOX2(dtc12 3 the MoOX2(dtc)2 compounds
of
been
CMoO(dtc)
with
nitrido
low
of
(2. = O,N,NPh; The
x=
(R = Me,Et,iPr,nBu;
reaction
number
13Oppm The
the
-
solution_ about
WO(OR)2X2
by
a Large
dependence. about
so there
same,
and MoLX2(dtc12
in dichloromethane span
the
= 2_123(8)'A(av)
c511.
compounds been
= 2.014(5)
MO-N
= 1.971(7)
WO(OR>2C12
The
w.4)
complexes
frequency
of
MoN(dtc)3
their
0x0
have
analogues
showing
95Mo c531.
46 Dimeric
2.1.4
There and
on
with
Raman
comphxes
and
FTIR
groups
Both
types
interact
with
As change
the
with
suggested
that
diagnostic
of
is
crystal
determined. in
is
very
the
configuration
of
the
of
for angle
from
/o\+N ’
structure
Mo(VI)
increases
species
identities their
their
g5Mo
NMR 0x0
on
0x0
groups
to
that The
1983. the
[Ma2051
tridentate
gave showed
/ \/ M
/ MO -
0
is
oxygen
compound
the
stereochemistry
The
angle
The sequence
Mo=O
=
l-713(8)
MO-O
=
2.018(6)
=
2.353(7),
at
the
in
the
bridging solid
interaction of
MO(W)
been
a facia2 C563_ (HL)
\ MO
Mo205L2(dmf)21.5H20.
/
shown
in
0
(23).
\
3 -
\
(23)
A
\
N
\
/
followed
/
are
Mo-O(dmf)
asymmetric
C551_
adopts
0
0
[541_
core
147.0(5)O
the
-
0
0
monomeric
for
has
ligand
dmf
dmf
alumina,
groups
I
0
distances
the
2-o-hydroxyphenylbenzimidazole
dmf/H20
monodentate onto
120ppm 2+
species
Mo205(Me2CH2CH2N(H)CH2C(Me)2S)2
bridging
with
determination
of
two
while
about
solution
bridged
oxalato
at
bridged
0x0
with
monodentate signal
in
absorption
I
Bond
oxalates
dimeric
monomeric
via
via a
the
Mo205(Me2NCH2CH2N(H>CH2CH2S)2
at
Mo02(acacj2
recrystallization
to
a mono
similar
review
and
Reaction
surface
structure
It
described
the
of
pH
their
surface
interact been
study the
retain
has
complexes
crystal
0x0
alumina.
oxalato
dimers
The
a onto
groups.
It
by
been
chelated
species
0x0
has
absorption
oxalato the
and poZynerZc
reactions
(PPh4>2fMo205(SC6H40)21
=
1.855(8),
MO-N
=
2.204(av)
oxygen
is
165_4O
and
the
w h ose
the
bridge
is
distinctly
c571.
(PPh4>2cMoOS3(CuCl)31
but
l-906(8)
2.390(7)x
state
of
MO-u0
only
with
product
structure
so is
far
shown
KSPh
in
MeCN
characterized in
(24).
gave is
a complex
47
MO
S-
Bond
distances
u-O(ligand) highly
= 2.117(2),
bridges
oxygenated
Interaction L-valine, MOTORS
S
MO -
= 1.705(2)(w)
MO-uO(ligand)
this
-
0
are
Mo=O
The
-
are
DL-valine which
asysnnetric-
species
of Na2CMo04] etc) are
2.482(2)
It
is copper with
in H20 thought
amfno
at pH
MO-u0
catalyzed acids
to have
the
\
that
gave
the
structure
!o/o\ll/,o O\
c-/o
OH
I CH(R)
I NH3+
of
(25)
L-alanine,
complexes
(25)
0
/\
formation
(LH = glycine,
MO HO
the
[58].
(LH)
2 at 80°C
0 0
thought
is
= 1_929(2)'A
in which
the
amino
48 acid
in the Zwitterion The
from
compound
the mother
be made
more
form
bridges
K6~W4Og(O2>6(CO3>1_6H20 liquor
was
in the preparation
rationally
from
showed
a new
crystallography
the metal
atoms
c593.
first
obtained
as a by-product
of K2[W0(02)2(ox)],
and H202 K2C03 tetratungstate(V1)
but
[W0412-,
in water,
type
as shown
it can
also
X-ray in
(26).
0
-0
0
0
\
\/
\
“c
O
/
,4,0vL
O\,
/
\oOo’ll\
o(i
0,
I/O
G”,
0
\
(26)
o//7(---
“\ A\
o-
Average
bond
distances
w-0
The
structure
are
seven
have and
tungsten
only all
peroxo)
oxygen
Reaction in acidified
= l-95(5)
W-O(eq)
= l-98(318
of
a parallelogram
bridged
group
atoms as
W-O(02~
= 2.21(3)
tungsten
peroxo
tungsten
= l-70(41
consists atoms
coordtnate; one
an 0x0
black
X-ray in
short all
units bridging
MO-N
suggest
1 and W2
group
3 which
distance, multiple
are
and W4 have axial
atoms All
with
the
bridged two
together
with
crystals
(NHEt3)2~Mo204(OMe>(NNPh)21~
bidentate
tungsten ligand.
by
peroxo
with
two
tungsten the
atoms
carbonate
groups
another
each
(not
[60]_
yielded
structure
of
carbonato
Atoms
tetranuclear &s-M~(NNP~)~
the
atoms
each.
have
shown
by
of Mo02(butane-2,3-diolatej2 MeOH
0
are
W-O(ax>
opposite
0
shown
bridged groups.
the N-N bond
diffraction
Mol-Mo3
distance
order
of empirical
(27).The
by methoxy The
excess
groups
and
the
in the MO-N
the
geometry
and
distance
two
and
N-N
anion may
[M004]~-
suggests linear
and NEt3
formula
showed
overall
phenylhydrazine
to have
be viewed units
no MO-MO
nature linkages.
of
the as
acting
bonding.
the MO-N-N The
two
electron
as The
unit
49
Ph \
N
N
/Ph
I’
/ N
(27)
N
PhlN Ph
Bond
distances
are
.Mo3
=
3.465
MO-N
=
1_823(9)(av)
Mol..
count and
is
consistent
therefore
oxidation
the
state
various
Thus,
with
of
products MeOH
in
of
the bond
former
was
distance
W(NPh>C14
ligands
coordinated
with ox+ygen donor
1,227(12)g(av)
acting
as
molybdenum
three
atoms
electron
are
donors
formally
in
shown
reacts
2,3-dimethyl-2,3-butanediol
to
of
various the
alcohols
steric
be
the
as
in of
(28). a
presence (pinacol-H2,
The
triple of
dimeric
Cl ] 2 22 W-N-Ph
bond
the
presence
of
the
of
with to
give
base
alkoxides.
species
were
formed,
group
is
The
linear
structure and
the
C621,
N('Bu)~ L-H21
in
requirements
the
@Bu)NH2
[W(NPh)(p-OMe)(OMe)
suggestive in
with upon
presence and
is
Zigands
W(NPh>C14
depending the
[W(NPh>(u-OMe)(OMe>312
W-N
diazenido
=
[61]_
interaction
gave
the
octahedrally
(0)
2.1.5 CompZexes
The
with
N-N
two
moles
three
of
products,
WL3,
50
OMe
OMe
Me0
OMe
,N
Ph
tie OMe
Bond
distances
are
w I.. w 'W(u-O)(~?rans
NPh) w-o
W2(NHPh)L5 WL3.
The
that
of
and
OMe
= 3.467(4) =
W(u-0)(&s
2.16(2)
crystal
structures is
=
l-61(4)
NPh)
=
2.05(2)
= 1.90(2)Z(av)
whilst
W2(NPh)20L2(L-H)2,
W2(NHPh)L5
W-N
shown
of
the
in
(a)_
a
latter
larger two
amount
compounds
of were
I-0
“Q/O-\ O'bN-" 0
Bond
distances
Ph
/
are
W-N
=
2.02(21
w-0
=
1.80(2)-2.00<2)'A
pinacol
gave
determined
only and
51 The
W-N
distance
the
protons
of
determination The
is not the
consistent
proposed
they
were
compound
with
NHPh
a triply
ligands
observed
were
in solution has
W2(NPh)20L2(L-H>2
not
NPh
resolved
'H NMR
by
the
bonded
group in the
and
structure
spectroscopy
structure
shown
in
although
C631_
‘;
n
“-O\/O “\ /O> o-w-
N
O-?“\OCm)
“\ Ou”-Ph
Bond
distances
are
W-N
= l-75(5)
w-u0
N)
= 2.30(3)
w-o
w-o(tmns
The
W-N
distance
is very
oxygen
tansto
be
protonated
the
Self theory
levels
systems
the
S-S
Reaction resulted mole
the
are
lowest
levels
and of
equivalents I
551
for
very
a triply
long
W-O
bonded
bond
NPh
distance
ligand.
The
is assumed
to
and suZphur donor complexes
have
with
been
earlier
of
found are
the
isomeric of
performed using the local density 22the anions, For cMoS41
[Mo3Sg]
MO-S
high
absorption
bonding,
and
the
of
(Me3Si)2S,
was
isolated
The
(or:g_7:1)
cage
and
partial
a compound which
X-ray
bands.
the
weakly
MO d-orbitals, mixture
but
calculations,
to be Mo(V1)
non-bonding
an
in cleavage
(NBu~)~CMO~S~ _4502
the
[MoS4] 2- and
re-assignment
molybdenums
antibonding
eight
for
are in accord
require
terminal
with
typical
= l-82(4)-2_00(5)g
[631.
calculations
method
calculations
and
thiatungstates
consistent
(LDT)
group
oxygen
ThCnnoZybdates,
2.7.6
MeCN
the NPh
short
= 1.89(4)
of
central bonding LDMO
the
energies
For one S-S,
cMo3Sgl Mo(IV).
of 2-
the
, the
In both
weakly
is MO-Sx * [64]_ 4with (Me3Si12S
[MogOa61 reduction
with
of Mo(VI)_
empirical
formula
crystallography
showed
With
to
in
52
consist only
of in
almost
the
equal
identity
amounts
of
one
of
CMo3S8021
terminal
'-
ligand.
and
The
[Mo3S70312-
which
structures
are
r
differ
shown
in
I 2-
O\\
/\
/\
s,qMo2,
//o’s
,M*‘\
/Ho3
~
<311
Bond
distances
are
Mol-Mo2 Mo2=0 Mo2-S(S2) s-s
The
central
(VI),
The led
atom
95Mo
to
and
is
=
2.896(l)
Mol-Mo3
=
3.047(l)
=
1.677(S)
Mo3=0,s
=
2.395(3)
I
2.051(4)%
oxidation
l7 0 NMR
reactions
of
dinuclear
The
in
The a
in
MeCN.
dark
This
one-electron
MoBr4
is
the
that
of
a
of
of
to
outer
ones
MORBID
X-ray
two
from has
state
SMe2
and
the
COAX
gave
complexes
solution
the
ligands-
and thf
4gave
interaction
of
was
iron
a
almost
compound
cubane
which
Electrochemical
reversible anions
[68],
a dark
brown
Mo2C02S4(Rt2dtc)2(CO)2(MeCN)2
distorted
[MS4]2-
(NEt4)2[MoS41
series
pattern
and
2-
the
of
extensive
MoS4
in
by
solution
powder
the and
[673_
prepared a
oxidation
corresponding
MeCN
the
with
measured
corresponding
chelating
one-electron
complexes been
with
Its
the
in
iron
was
MeCN
in
Mo2S4(Et2dtc)2
showed
in
type-
give
oxidation
have in
derivative
by
2,898(6)
and
of
characterized
surrounded
Recrystallization crystallography
this
fully
reversible
reduction
a number
delocalization
cobalt
or
c661.
(NEt3H)SPh
first
iron
2_287(3)-2.458(2)
and
(NEt4)3[Co(MoS4)21
and
the
1.646(14)
=
C651.
[Fe3S2(WS4)3]4-)
electron
of
the
=
MO-uS
(PPh4)2[S2MoS2MoBr3(SMe2)1
compound
CoCL2
Interaction
X-ray
of
of
revealed
product.
with
spectra
compounds to
tetrahedral
studies
Raman
green
heterometallic
has
reported
respectively
terms
solution
identical
and
also
CFe(B20)2(WS4)212-,
discussed
of
(IV)
were
(PPh4j2fMoS4j
complexes
resonance
(e-g_
state
studies
(PPh4>2cS2MoS2Mo(NO>2Br21
ions
S
S
S
structure
which
53
co \
\
co co
I/ -S
/I
S
co
S
/
s-
S
MO
( ‘I
4
-MO
S
-S
‘I
(32)
PieCN
S
Bond
distances
are
MO-MO
MO-pS(Mo)
original
lengths bond
are
length
very
unit
similar
of
the green
Similar but
reaction
reaction
structure
seven
with
of
2-
the
useful
complexes route
to
+tInds
starting
the MO-MO
and MO-lJS
material.
The
the MO-uS(Co)
(33) type
-
W
VI
molecule
with
tmds
gives
linkage
original
bond Mo=S
C69I. (tmds)
causes
a
S(S2)(S2CNR2)2
structure
whose
gives
reduction
MoS(S~)(S~CNR~)~
is shown
to MO(V)
which
(see
Ls known
in <33). later),
to have
a
c701. Mo(L-L)2(deazjn
diethyldiazenedicarboxylate) These
and
tetraalkylthiuramdisulphides
coordinate
[MoS4] . CMo02S21Lto
similar
Compounds
= Z-316(1)
reaction
of
with
in the
it becomes
cwVIs412-
to give
MO-vS(Co)
is recognisable
to those as
CWS41L-
redox
= 2.680(l)
= 2.533(1)X
is increased
based
MO-CO
2.788(l)
Mo2S4(dtc)2
Reaction ligand
=
= 2.360(l)(av)
CO-CO
The
MeCN
readily react 18 0 complexes
are
(L-L
readily
prepared
stoichiometrically 180Mo(L-L)
2
and
= dtc, from with
dtp;
deaz
Mo(CO)~
and
180 Mo(L - L) 2 1711,
2
= and
deaz-
so provide
a
54
s
s\
0/
s\u
CNR2
S’
(33)
I
Bond
distances
are
w=s = 2.136(l) w-se21
Anilinium-g-octamolybdate of aniline
crystals
were
presence
of
EtOH
gave
slowly
a purple
which
moities
with
to the
three
environment.
2 units
the
hydrogen
alternating crown
bonding
the anion,
EPR
spectra
proton
transfer
It is suggested
photochamical 17 0 and
reduction 183 W NMR
Na10 [H 2 W 12 0 42 l.27H20 change with pH and
that
confirmed
The
the
phenylhydrazine
of
and
NEt3
(NBu4)2[Mo8020(NNPh)6]
a crown
of
six oxo-bridged
MO
three
types
resemblance
reported)
to that
by replacement
c731.
of WV
irradiated
localized
of molybdenum the
precursor
of
three
(NH3Me>8~Mo8026(Mo04>23‘2H20
MovO
the
of
cation BCMO~O~~(MOO~)~I
(OH) sites resulting from a 5 to a bridging oxygen atom in undergoes
a four-electron
[74]. spectra
and are
the (pH 2.5).
and cis-[Mo(NNPh)212+ [Mo04122CM0041 units acting as trtdentates
giving
from
which
excess
units
two distinct
through
in water
[72].
showed
a close
is also
isolated
of Moo3
crystals
two more thus
bears
structure
of
which
by
centres,
by c
crystal
with
oxomolybdate
capped
structure
formation
anion
crystallography
Mo(NNPhj2 The
Single show
the
from
been
crystallography
@-[Mo~O~~]~-
solution
are
has
solution
a-(NBu4)4[Mog0261
X-ray
(whose
EMo~O~~I~&S-MOO
an aqueous by X-ray
known
between
separated.
centres
dihydrate
with
characterized
the well
Reaction
= 2.454(l)-2.528(2)
po tyanions
Homonuchar
interaction
W_S(dtc)
= 2_208(2)5(
s-s 2.1.7
= 2.588(l)
W-S(ax> 2-403(Z)
= 2.366(3),
have
been
Na6[W70241_14H20.
fully
consistent
obtained The with
for
acidified
spectra
the known
of
solutions
[W702,+16-
solid
state
of
do not structure.
in
'Paratungstate to those
2.1.8.
of
formed during condensation of [WO,]*- has spectra identical 6as previously thought [75]. [W7024] , so it is not a hexatungstate A'
HeteronucZear
A 31 P NMR
poZyanions
study
has
H*/[MoO~]~-/[HPO~]*-
system.
pentamolybdodiphosphate their
degree The
dynamic
anions
tridentate
ring
bonds
whilst
involves anions
or
two
of
example
a g-type
of
atoms
in the
a single
exists
whose
by a common
groups
on
members
processes,
temperature
MO-O
ring
side
the and
low
of
differ
capped
the
only
by
one
features
of relatively
although
processes
The
by
ring_
temperature
making
process,
Similar
bonds.
Mo6018
either
the breaking
of
octahedra
which
6 the
and
isolated general
not
occur
long
fully for
MO-O
defined,
the
other
linked
family
groups
by
of
sharing
is completed
revealed
three
by X-ray
the
corners.
first
The
W06
octahedra
and
One
As
central
to three
by a hydroxy
CaC
compound
of polyanions-
is linked
heteropolyblue determined
in the
determination
the other
sphere
structure
isolated
is the
outer
group
oxygen
[78]_
5[H6M~12040]_18H20 * diffraction_ It has
as the 8-[SiW 1 14- anion C791. l4 12 40 anion [NaP5W3C01101 - is formed as a by-product in the 6and has been characterized by X-ray crystallography.
one
has
been
the
same
structure
The
cp2W180621 approximately
the Na+ plane Line
encapsulated appears
its
sharing
while
reduced
been
the As III/W
edge
are
heteropolyanion
has
structure
for
two
its coordination
and
anion
A crystal
A four-electron
four
equilibria
Mo/P<2.5
complexes
dynamic
structure
is composed
two wo
the
the
[76]_ 4the a-[Mo80z6] , [(PhAs)Mo 0 14- and 17 ' 25 0 NMR spectroscopy_ been investigated using
8-tungsto-Z-arsenate
of
structure
with
and
related
strong
on
the pH varies
higher
K7~AsW8030As(OH)~_12H20_
atom
of
involving
second
cleavage
pH>5.5
[PhAs0312-
inversion the
have
out
C771.
A new
of
of
anions
- shows
c(PhAs)M0~0~~1
as
structurally
CMO~~I~-
Mo6018
series
behaviour
are
carried At
of protonation
[(PhAs)2M0602414three
been
D5h ion
symmetry located
containing (2:Z:l:l) and
the
anion
five
lg3 W NMR
does
not
to be necessary
interesting
and
and
consists
within
some
phosphorus spectrum
exchange
for
of
a cyclic
the polyanion
the
in solution.
formation
with of
array
the This
atoms.
readily
vanadium
on
the
substitution
anion, products
and
but
gives
sodium
Na+
PW6022
axis,
asymmetry
of
It has
five
fivefold
The
free
of
synthesis
ion
units above
rise
to a
is tightly
its presence
Reduced were
forms also
of
this
described
C801What
is thought
K28Li5CH7P8W480184 crystallography.
to be
1_92H20,
the
largest
has
been
It crystallizes
known
prepared
spontaneously
phosphotungstate, and
characterized
from
LiOAcjHOAc
by X-ray buffer
solutions
56 [H P W 0 1 which is Of K12 2 2 12 48 degradation in the presence
itself of
obtained
amine
from
according
by
[P2W1806216to
the
scheme
alkali
(34).
CQ2-P2W170611
t
lo-\ lo-
cal-p2w170611
(34)
The
structure
linkage
of
of&_four by
EP2W180621 four from
the
The
in "
in
solution
species
V
the NMR
to
the
tungstate " 0
being
in
P:V:W
a
are
in
the
form
derived
adjacent
of
a
from
W06
crown
the
formed
well
octahedra,
by
known
two
from
the
structure the
cap
of
and
cSl1. series
ratios
of
of
dependent
solutions
l:6:6, The
spectroscopies.
2-
+
was
upon
of
1:8:4
sodium
and
compositions pH,
but
1:10:12 of
no
phosphate, have
the
vanadate
been
and
studied
by
vanadophosphotungstates
solution
ever
contains
just
one
NMR
spectra
confirmed
the by
of
species
of
the
structure
surface
yellow
from of
The
[W041 two A
to
-
heteropolymolybdate 2-
and
cp2TiC12
compounds
based
on
are
that
changes
and
charge
+
2[cpTi(Mo5018>1
and in
very
crystallographic
resultant
activation
3-
+ H20
the
simple_
cpTi.
reaction
2cp2TiC12
prepared
Mo=O
unit
the
formation
particularly
terms
six
polyhedra
dichloromethane
5CMo2071
and
of
loss
is each
[821.
In
led
the
formed
tungstate 31 P and each
P2W1204g
subunits
belt
ions
33-
[H7P8W4801841
the
acidified
similar,
study of
CMo60191
in
the
on 2-
bond
delocalization
2C5H6
CH2C12.
The
the
NMR
molybdenum
with
were
these
IR spectra
compound
replacement
lengths in
4Cl
corresponding
with
the
+
of
and
in
similar
[831_
Reaction
of
Na2[W041
and
ZrOCl2
followed
by
addition
of
NMe4C1
gave 183
Various
(NMe4)2[H2ZrW50191spectroscopies [W601s1'-
one
discussed
were
all
physical
consistent
measurements with
a
including
structure
IR,
analogous
UV
to
and
that
W
of
[841.
Addition
of. (Me3Sij2S
to
(NBU~)~CM~W~O~~I
(Mq
= Nb,Ta)
in
dry
MeCN
gave
NMR
57 (NBU~)~CM*W~CI~~SI complexes The
is replaced
I7 0 NMR
spectrum
in solution
terminal
was
fully
to be isolated
was for
_ A crystal
the heteropolytungstate but
atoms,
structure.
an ONb 2 oxygen
and
oxygen
II) or
(isomer
shows
isomer
solution
2.1.9
two ONbW
OW2
retention
the
metal
are
were
possible
(isomer
oxygene
I>,
other
structure
0
[851_ (M' on
= Mn,Re)
the Mn
contiguous
disordered
with
d
M'(C0)3
to
compound
bridging
in the
solid
coordinated
to
two ONbW oxygens and one OW2 ;17 III>. 0 NMR spectroscopy
(isomer
both
three
same
first
determination
to Mn by
original
cryetallography.
fac-[M'(CO>3(MeCN)31Cl
in the cluster
but
of
is the
transition
structure
oxygen6
three
in the
by X-ray
This
an early
dietereoisomers
II to predominate,
isomers
are
also
present
in
C861.
Complexes
The
with nitrogen
unusual
MoC14(MeCN)2
complex
with
interaction
showed
with
observed.
with
metals
at Nb or Ta
confirmed
coordinated
the heavy Three
wae
consistent
resonance
1 reacts
state
oxygen
This
sulphur.
(NBu4)4tcis-Nb2W4049_
oxygen
shown
the
C(CO>3M'[Nb2W40191
showed
the
by
as no M'=O
polyoxothioanion
give
in which
and
of MoC13(terpy) a seven
(35) with
phosphorus
donor
MoN(C1>(N3)2(terpy)
Me3SiNj
it to have in
and
subsequent with
and
formed
addition
Me3SIN3.
coordinate
the nitrido
was
of
either
terpy
A crystal
pentagonal chloro
2 igands
axial
or alternatively
structure
bipyramidal
ligands
by reacting by
determination
stereochemistry
as
1871.
N-N-N
N-
Bond
distances
MO-N(N$ MO-Ncterpy)
strong
bans
N
are
Mo-N(nitride)
The
N-
effect
= l-662(7) = 2.076(7),
MO-Cl
= 2_719(2)
2.114(6)
= 2_235(5)-2.285(6)x
of
the
triply
bonded
nitride
causes
the
long
MO-CL
bond
58 distance. Various
mixture 13 C NMR
pinacols
of
reacted
with
(pinacol)W(NR2>2(NH2R)
studtes.
although
were
not
However,
the
in
isomer
same
(RN)2W(HNR)2
and
the
solid
for
each
(R
= 'Bu)
(pinacol)W(NR)(NHR)2 state
each
pinacol
shown
in
a
give
by 'H and
as shown
pinacol
as
to
gave
only
one
(36)
and
(37)_
isomer,
NR
RNH2 I
II
RHN\W cF3
o
RHN’
cF3
CF3
I 0
cF3
2
CF3 CF3
(37)
(36) R
Bond
distances
tBU
=
are
(36)
The
tungsten
(38)
imino
considered
to
used
been
W=NR
1.742(3)
1.753(4)
W-N
2.201(4)
1.927(4)x
atom
the
in
each
groups
are
be
for
ammoxidation reactions
investigated by
PhC(O>NHNH2
of
and X-ray
provides
together
short,
atoms
were
quite
showing
trigonal
for to
structures
first
of
located)
significant
(X two
of
as
CBS]. with double
bond
in
0,s)
the
and
bond
(38).
distances
character
are
catalysts
PhC(X)NHNH2
products
hydrazido
diazenido
in
molecules
heterogeneous
of
group and
have
been
'end-on'
It
for
group the
NHNHR
a N2C(0)Ph (for two
distances
electron
and
bonded
contains
(I-)
bond
have
Mo02(PhC(S)NMe0)2
characterized
shown
The the
These
[881. =
interaction
NHNHC(O)Ph
stereochemistry,
(37).
molybdenum
structurally
the
in
acrylonitrile
The
molybdenum with
different
the
Mo02(PhC(X)NMe0)2
the
for
bipyramidal
axial
but
models propylene
the
group
are
a
crystallography.
diazenido(2-) hydrogen
has
equatorial,
between
hydrazido(l-)
moities
case
homogeneous
The
determined
(37)
which
the
hydrazido being
delocalization.
quite
59
Ph
0 *
c’
/ Ph
N4
\
S
C-
/
/
N3 I -
/
MO
7 -
y5Ii
Ph
N6 ‘C
s
1
I MeANY \ Ph
Bond
distances
are
MO-N3
=
1.758(5)
N3-N4
= l-292(4)
#o-N5
= 1.938(4)
N5-N6
= 1.361(7)
MO-O
Reaction
= 2_106(av)
between
MO-S
Mo02(PhC(S)NMe0)2
Mo(NHNC(S)Ph)(N2C(S>Ph)(PhC(S)NMeO) structure
shown
The give
in
complexes
showed
molecule
is rigid
signals
spectrum
red
[MC1(NNMe2>2(PPh3)21Cl
it to have
and the
in solution
purple
indicated
confirmed
porphyrin
other.
was
shown
gave
to have
the octahedral
react
a structural
pentagonal as
shown
with
PhP(CH2CH2SHj2
determination
on
in MeOH
to
the molybdenum
bipyramidal
structure <40). The 1 31 two non-equivalent P and H NMR
by
1901.
The
study
which
PhC(S>NHNH2
c891,
M(NNMe2)tPhP(CH2CH2S)2}2
compound
the
and
e 2.445R(av)
They
and,
2,086
2.0928
1.909(15IZ(av)
The
atom
the trans
nitrogens
for are
tungsten the
distances
of
2,298
the others.
normal
[913.
has
been
porphyrin
as a result,
eclipse
W-N
W(TPP)(0)(02)
an unsymmetrical
this.
different and
complex
0x0
of
to one
peroxo the
and
2-87851 f or
The
W=O
and
and
coordination
is 1.492 and
isolated
groups
porphyrin the
W-0(02)
and
side
its 'H NMR a structural
of
the
are &a and
eclipsed distances
this
N4
leads
nitrogens of
plane
of
to each to very and
l-752(13)
and
Ph
\
c
-N
\
s,i->s\ I
,/i”\N_.i”-ph
Me
- /‘c
S
/
N
<=I
I Ph
Bond
distances
are
Mo-N(NN)
MO-N(NHN)
= l-789(4)
MO-O
=
= l-972(3)
MO-S
2.051(3)
= 2.436(l)-2.504(1)x
Me2 I N I
Bond
distances
are
MO-N MO-S(PX) MO-P
= l-775(6) = 2.499(3) = 2_517(2)~(av)
N-N MO-S(eq)
= l-265(9) = 2.498(3)-2,548(2)
61 Oxidation CRC13
gave
WO2Br2L
cw*05L21*+ observed
of LW(CO)3
which
whose
made
this
by
with
slowly
direct
of
with
cont.
acid
to
of L'Mo(C0)3
Somewhat
first
yielded *+
with
excess
bromine
it transforms different
in
to
chemistry
is
L' = N,N1,N'm-trimethyl-l,4,7-
gave
CW205L’23
with
In solution
c921.
(where
bromine
nitric
hydrolyses
oxidation
bridge
L'M(C0)3
Oxidation
oxidation
fs unknown.
a monoxo
oxidation
triazacyclononane),
tungsten
structure
contains
in the
further
(L = 1,4,7-triatacyclononane)
[L'M(C0)3Br]Br
[L'M02Brl+. 193,941
more
on
In the
case of 2+ was ~Mo~O~L'~~
while
dilute
which
HN03
[951.
The
crystal
?*
structure
of
1~1LT was determined
CMo205L
and
is shown
in (41)_
2+
\/\ L distances
The
compound
In the
Mop0
= l-695(7)
PO>
= 2.290(9)
Reaction colourless
unambiguousLy
be reduced of
1.73BM
reductiona
tungsten
one-electron
of
can
moment
one-electron
0
(41)
A
0
are
MO-N(tma
magnetic
N
MO -
N
N-
Bond
o-
MO -
.N -
system
chemically per
are
both
reductions
= 1.898(l)
.s-
0) = Z-325(8),
to the deep
molecule.
seen
blue
2-355(8)A
+1 cation
ElectrochemFcally,
two
which
has
a
reversible
[951
cL'W02Xl+
and
[L'2W205]2+
show
single
reversible
[94].
of WC14(PMe3)4 WH6(PMe3j3.
MO-u0 MO-N(trans
The
as the molecule
with
LiA1H4
structure
in ether in solution
is fluxional
and
at -78OC could
crystals
led not
to the
fsolation
be determined
suitable
for X-ray
62 diffraction
could
not
be obtained.
NH2($J1-C2CH)()J2 -02CH)(PMe3j3 wide
temperature
bidentate
range.
format0
whose
The
groups
spectra
and
AND
also
2.2
MOLYBDENUM(V)
2.2.1
Halides and halo complexes Chlorination
the
product due
to MO-Ft
chain
structure
temperature consistent
at
with
Interaction monomeric
MoCl
structure
(42)
4
sealed
in the cooler 720 and
exchange
680cm
tube
region -1
of
per molybdenum
and
decreases
exchange and
in a polymeric
and
X-ray
’
The
and
crystal
shown
in
The
and
with chain
and
E961.
MoF3C12
with
IR spectrum showed -1 _ A polymeric
446cm
moment
temperature. structure
in CC14
diffraction
showed
at room
This
is
[97].
suspension
Ft to have
gave the
C -Cl
1
'N'
(42)
are
MO-N
= 2.079(4)
N)
= 2.266(l)
in dichloromethane
MO-Cl(c&
reacts
(PMePh,)2[Cl,Mo(p-S2>2MoC141_2CH2C12_ MoBr4
a
E981.
MO-Cl(i%ans
from
gave
The magnetic
diisopropylcarbodiimide
(ZPrNC(Cl>NZPr>
Cl
Mo(S2)C13
tube-
at 494
b suggested.
MO
distances
over
monodentate
exchange
120-150°C
the
and MO-F
cl\I/N\
Bond
at
was
of MoC15
studied
between
site
bridging
magnetic
.
in a long
fluoro
is 1.29BM with
indicated
phosphinelhydride
were
TUNGSTEN(V)
of MoF3
condensing
bands
Reaction with CO2 gave 1 31 H and P NMR spectra
S7NH
and
structures
(43). The
The
subsequent of both
MO-MO
addition
were
distance
with
3 corresponding of
determined,
suggests
(PMePh
N)
>Cl
they
to give bromo
(PMePh3)Br
a single
= 2.343(l)%
are very bond
complex
in CH2Br2
[993.
similar
was
made
solution. and
are
63
S
Cl
cl\\ //q
/p
Cl
2(43)
clq”\qM\ Cl
Bond
distances
Cl Cl
:
are
2-
2-
[Mo2(S2)2C181
MO-MO
2.875(l)
2.855(4)
MO-S
2.422(1)-2.429(Z)
2.412(6)-2.424(6)
MO-X
2.407(l)-2.518(1)
Z-566(4)-Z-688(3)
s-s
1.981(l)
1.969(9)x
Trimethylsilyldialkylamines, (1:l)
MoOC14
in
aprotic
complex 2:l
solvents
MoOC14
but
such
excess
+
Interaction crystals
of
salts
in
+ 2
Me3SiNR
causes
3Me3SiNR
+z
of of
PPh4Cl the
or anion
moisture.
X-ray
crystallography
structure
<44)_
The
structure
product
the
reaction
the
is
to
with
of may
the be
compound
regarded
ClOO,lOll.
At
is
occur
+
to
give
2 Me3SiCl
Mo(IV)
+ Me3SiC1
+
with with either
the R as
oxygen
=+-tolyl a grossly
ClOll.
(Me3Si)20
(Me2S)C13W(SR>2WC13(SMe2)
[C120W(SR)2WOC12]-
with
tetraethylhydrazine
(MoOC13)2tds
MoC~~(NR~)(NHR~)~
AsPh4C1
react
compound
+ Me3SiCl
MoOC12((NR2)(NHR2)
transfer
+2E!
Et2,pip,pyroll) a MO(V)
gives
the
+H -
2
=
give
MoOC13(NHR2)
Me3SiNEt2
CS2
oxygen
2
to
2
CC14,
CR2
ether
dichloromethane
Me3SiNR2
MoOC14
as
while
in
or
+ Me3SiNR
MoOC13(N2Et4)
proportions
Me3SiNR2,
dichloromethane
MoOC14
In
[Mo2(S2)2Br81
gave coming confirmed distorted
from the
r
Cl
/
0
Bond
distances
W-W
confacial
2.878(Z)
w-s
=
2.427(3),
W-uC1
=
2_604(7)g
bioctahedral
or
as
filling
crystal
two
the
structure
Oxidative
of
Interaction
is
this set
up
addition of
the
formed by
of
latter
square
pyramids
octahedral the
(pyH>2[Mo203C14(OEt)(HOC6H4C02)]
MeCN
0
= 2.378(9)
=
interactions The
p-to1
are
w-cl
W-Cl
’
H2
at
with
known
60°C
to
TlCBF.1
and
WC12(PMe3)&
is
as
gave
~lcl~
gave
MeCN
the
In
edge
ti
crystal described
analysis.
structure as Bond
of
+e --f
in
(45)
[WH2C1(PMe3)4]+ square
[103].
and
in
scheme
reaction
(461
+
CwH2C12P43
tS MeCN
MeCN
CWH~C~~(PM~~>~~(BF~)
dodecahedral distances
long
WH2C12(PMe3)4_
(46)
EWH~CIP~(MGN)
be
two
oxidation-
WH2c12p4
The
with
complex
determined
or
an
[102].
salicylate
been
~~2C1(PMe3)4(MeCN~~+.
electrochemical
sharing
positions
has
2.450(3)
are
but
the
W-Cl
=
with
U-N-O
was
hydride 2.438(6)
12+
determined
ligands
were
and
=
W-P
and not
the
cation
detected
may
in
the
2-482(6)-2.595(5)x
c1041. Tridentate
Schiff
Prepare
MO(V)
MoOCL2L
with
magnetic
ligands
gave
dinuclear
have
severely
complexes_
depressed
bases The
O-N-0
moments complexes magnetic
of
and
donor
N-N-0
ligands
approximately Mo203C12L2 moments
donor (L)
gave
1.7BM.
The
thought ElO51.
sets
to
be
have
been
monomeric N-N-O 0x0
used
to
species donor
bridged
set and
which
0
Et
0
A\ II ‘I
1/
CI
2-
/
MO
Mb
I’
(45)
\ Cl
O\y/
0
/b
OH
I
Bond
distances
are
MO-MO
= 2.646(2)
Ma=0
MO-JIO = 1.912(av) Mo-O(sal)
A serles Schiff
base8
prepared
of
various
by reacting
to be dimeric
with
Mo-VOEt
= 2_306(14)(av)
of complexes from
the
alkoxide
= 1.964(10)
MO-Cl
type
substituted
(N)14)2[MoOC153 the
= 1.670(14)
MoOClL
= 2.399(S)-2.432(6)%
(L = tridentate
salicylaldehydes and H2L
oxygens
and
in EtOH.
acting
0-N-O
The complexes
as bridge8
donor
ethanolamine) are
as well
were thought
as chelating
11061_
2.2.2
I&nomeric
The organic monomeric to give compounds changes of
visible solvents
0x0
compZexe8
absorption have
been
in dichloromethane CM~O(TPP)(~IIISO~X
in the absorption disappear8
of MoO(TPP)X
solution.
in CH2C12/dmso
are photosensitive
MoO(TPP)X
spectra
investigated_
when spectra
a8
the
EPR
The The
axial
mixtures
irradiated suggeet silent
compounds
compounds
shown
is substituted
c1071.
In 2-Methf
reduction
region
to MoO(TPP). is generated
in
to be
ligand
in the Soret
MoO(TPP)
(X = F,Cl,Br,NCS)
were
by dmso
MoO(TPP)X and
the
The
EPR
ClO81.
signal
2.2.3
p-0x0,
The
p-sulphido
kinetics in
[Fe(phen)313+ the
rate
the
first
With
the
of
x
aquo
The
have
the
compounds of
solvent.
On
ligand
The
with
Mo(V1) of
it
complex
of
give
the
be
Mo(IV)
this
Solution8
but of
an
is
in
solution
equilibrium
the
MOOR
in
converted
to
(~~H>~~Mo~o~(Ncs)~~ with
water
the
the
with
L-L
with
0.5
yielded
it
was
does
not
obey
Mo(N-p-tolyl)(dtc)2
given
trapped
by
the
its
Beers
Law
The and
with
further
compound
is
PPh3
which
reactive
and
it
mixed
(0x)~(H20)~)
Mo(V)/Mo(IV)
with a
were
obtained
electrons
which
the
oxidation
mixed
presence A
of series
(c-hexyl)2)
were
oxygen of have
(monooxo
bridged),
bridged)
and
The
by
oxygen
catalytic
to
not
adduct.
reform
cycle
they
by
dimers rapidly
MO(V)
species
been
prepared.
M0204(R2C02)~
of
pulse decay
They
the
the
(t
MO(V)
carboxylates are
(dioxo
of
the
bridged),
(monooxo,monosulphido
(dmmp>OMo(p-O)(u-S>Moo(MeOH)
4,6-dimethylpyrimidine-2-thione)
has
been
(L
for
=
MO(V)
radiolysis. Slowly
reform with
2-
[Mo204Ln1
reduction
generated state
Mo203S(R2CO2)2
complex
complexes
is
gave
could
dimethylacetylenedicarboxylate
react completing
PPh30.
+ MoO(N-p-tolyl)(dtc)2
reaction This
as
Mo(N-p-tolyl)(dtc)2 thus
reacts and
the
oxidation
of
[1121. The
_
dissociation
Mo(N-p-tolyl)(dtc)2.
MoO(N-p-tolyl)(dtc)2, PPh3
by
of
cis-MoO(N-p-tolyl)(S2CNEt2)2
x
scheme
complex
isolated,
of
reaction
with -l/l 13M
is
prepared
were
=
clO91_
solution
compounds
k
constant
were a
species,
oxidation
[Mo(N-p-tolyl)(S2CNEt2)2120
dimer
undergoes
[Mo(N-p-tolyl>(dtc>2120
the
on
rate
that
process.
constant The
systems
indicates
a hydroxy
investigated
and
reaction
which
overall
the
rate
the
phen)
HF
these
Similarly,
to
PPh3
spectrum
for
bipy, 40%
water
and
both
for
order
also
In and
[1111.
that
Support
= in
25OC_
mechanism.
were
and
oxidant
involves
second
sphere 4+
(L-L
at
and
determining
sphere
outer
[Mo3041
dissolved
[1101.
oxo-imido
electronic
be
inner
[Fe(H20)613+
examined
a
Mo203(L-L)2(NCS)4,
equivalent
proposed
rate
with
an
by
reductant
pathway
and
digestion
Mo~O~(L-L)~F~ gave
is
Mo~O~(L-L)~F~
the
been
in
react8
to '+
[M02041~+
predominant
by
expected
[Mo202S21
order step
which
Mo204(L-L)2(NCS)2
mole
solution
transfer
is of
interaction
EtOH
of
first
complex,
CFe(phen)313+
in
is
oxidation
, probably
Oxidations
known
aqueous
[Fe(OH>1'+, -3M-1s-1
10
same
the
reaction
electron
probably l-3
of
comptexes
prepared
edta,(L-cystJ2,
dimers In 1
with
the 5
l/2 dimers
hydrated
absence
-10s)
of
but
in
cl131.
R2CO2-
CR2
general
=
Me,c-hexyl
formulae
bridged) (dmmpH the
and
Mo203(R2C02)4
Mo~O~S~(R~CO~)~
by
oxygen the
(disulphido
El141_ = interaction
of
6'7 Mo02(aca+
with
determination
excess
atom
octahedral
Bond
distances
and
MO(V)
= 2.180(7),
2.209(7)
distance
compounds
with
one
molybdenum
l-667(6)
=
t l-911(5),
l-933(5)
suggestive
bond of
of
lengths
this
type
with shows
it
known
type
a
single
refer of
to
bond
the
structure
the
extra
is
possible
the
been
with
simple
is
molybdenum
discussed
interacting form
compound
coordinate
have
ligand to
and
five
in
terms
both
metal
of
dimeric
adducts
cll51. of
have
the
been
prepared
reductions of
coordinate
tungsten
Dissolving subsequent
determination
the
the
They
are
atoms
addition
of
P2S5
thought
and
to
they
cyclic
CR2
= Me,Et,bz; show
the
two
(1161.
gave
structure
= pyrr,pip,
reversible
voltammetry
= morph,pip)
have
R2
the (48)
corresponding with
five
C1171. in
of a
(R
CMoS412-
timescale with
(NH4)2cMoS41
revealed
Mo~(S~>(~-S>~O~
on
Mo2Sq(R2dtc)2
from
W202S2(R2dtc)2
compounds.
in
is
shorter
W2S4(dtc12
sulphur
structure
(47)
= 2.535(6>2
examples
one-electron
and
crystal
2.320(3)
structure
Interaction
in
Mo=O
MO-N
Compounds 4-Memorph)
A
shown
MO-~0
coordination'
This
MeOH_
coordinate.
2.489(2)
The
'crevice
five
= 2.435(3),
Previous
atoms.
other
MO-S
bond
diamagnetic.
of
refluxing
= 2.660(l) =
Mo-MeOH
atom.
in
stereochemistry
are
MO-uS
MO-MO
the the
MO-MO
The
dmrnpH
revealed
dilute
(N3uq)Br
HCl
gave
stereochemistry
and
Mo~(S~)(~-S)~S~
apical
positions
solution
shown
a dark
(NBu~)~[Mo~S~OI, very
structures
as
gave
A
crystal
the
known
similar
to
with
disorder
in (49).
red
between
solution structure
oxygen
and
68
s\,ASlw \
S
/
I
/
c-
s
IS
/
(48)
\
S
\
\
s-c
S
\
/
RN
NR
2-
S
S
Bond
distances
are
Mo=O,S
MO-MO
= 2.811(l)
MO-W
= 2.307(3)-2.320(4)
= l-945(6),
MO-S,
l-986(6)
2.376(4)-2.398(4)x
= L
The
MO-MO
suggests, dimcr
distance
is
but
not
rather
does than
a
indicative
of
a
unequivocally
solid
state
single
bond.
prove,
mixture
of
the
evidence
Spectroscopic
existence
[Mo~S~O~]~-
unsymmetric 2anions [Mo2Sg]
of and
the
Cll83. Interactlon Spectroscopic the
to
complex those
compounds
are
this
unit,
core
EMS4]'-
evidence
tungsten
similar
of
of
useful for
with
S
suggested was
in
that
determined
other
M(V)
precursors example
dimers for
M2Sq(dtc)2
hot
thf
they and
is
yielded
have shown
containing the
preparation [1191-
the
similar in the
[M2S121
structures
(50).
The
syn-M2S2 of
2-
other
anions. and
that is
structure unit. species
of
These containing
69
2-
s
w\ \ I
w
/
s-s
I
\
s-
sLS
SAS
Bond
distances
are
w-w =
The
reaction
2.836(2)
w=s
= 2.116(5)
w-Ils = 2.320(6)
w-s
= 2.387x(av)
between '-
CMo202S2(SCH2CH2S)21 also
isolated.
they
are
The
very
phenylhydrazine
anion
crystal
similar
to
and
the
structures each
other
0,s
‘s\
“zC
II/\I1
and
MoO(SCH~CH~S)~
analogous of and
salts shown
distances
gave
of in
both (51)
anions
the anion
CMO~S~(SCH~CH~S)~I~were
2-
pcr2 s,C”2
are
MO-MO
02s2 Z-866(3)
s4 2.855(l)
Mo==O,S
1.659(30)
Z.lOS(av)
Mo+S
2.334(14)
2.313(2)
l-lo-s
Z-404(13)-2.418(11)
2.381(2)-2.412(2$
was
determined;
[1201.
0.S
H2L,s, MO\,/“O\
Bond
C50)
S
(51)
70
The
interaction
reduced
forms
distance
of
3.02%
observed
in
the
distances
of
were
xanthine was
distances
in
MO-S
=
2.545(2)x
MO-S
=
2.500(2)%
CMoS412-
reaction. the
the
series
assumes
of
is
=
2.418(2),
the
of
the
bond
The
and of
Bond
S4
EXAPS MO=&
iodine an
and
As
fully
Interaction and
A MO-AS
EXAFS.
the
was
Mo=O
interaction
oxidation
eight
forming
forming
in
Bond
a
an
and
Mo=S
disappeared
of
Mo2(Et2dtc)6
coordinate
flattened
cation
with
tetrahedron
elongated
with
tetrahedron
(33))
to
in
with
Mov(S2)(dtc)3 2corresponding [WS41
the
although
a
distances
2.445(2),
gives
However,
detailed
are S-S
=
give
in
description
Mo-S(dtc)
of
=
2.022(3)%
C701.
almost
are
the
in
certainty isomers
Their -1
IR
identical
W=O in
bond the
dissolve
in
PMe5)
in
small
number
which
one of
such
MeCN
contrast
form
by
bond
=
compound between
oxidizing
and
seems
to
M(III)
been
prepared
blue
and
green,
about
to
give
blue, the
stable
the
similar in
are
group
blue
and
yet
well
c921.
of
isolated
differences and
with
Interestingly, solutions
complexes
This
solution. not
(53)
determinations
green)
green
=
oxidation
been
only
C1241.
MoOC12P3
L
stretching
The
l-893(20)2
0x0
in
by
structure
tungsten.
atoms.
complexes.
have
W=O
diamagnetic metal
(where
shown
favour
have
crystal
structure
is
-trimethyl-l,4,7-triazacyclononane
L
is
always
1.706(6),
the
LW(CO>,
scheme
A
the
reaction
trams
which
(52).
overall
isomers,
to
in
ligand
N,N',N"
(1.719(18)
to
The
shown
The
single
[L'MOX21+
predominates
isomers
a
observed
geometry
distances
is
differ only in their -1 green) and crystal
960cm
faciaz
dry
in
interconvert,
spectra
distances
W-N
to
Two
blue,
scheme
states.
0 1(ClO > .2H 0 confirmed 24 42 2 are MO-MO = 2.586(l), Mo=O
with
compounds
[93,94,1241.
(980cm
showed
the
chemistry
oxidation
2.265(4)-2.346(4)A.
is
and
of
(I,) have
MO
consistent
pentavalent
EL1WOC121+.
frequencies
=
1,5,9-triazacyclododecane
reaction 2
substituted
different
compounds
the
chemistry
highly
the
a number
anti-CL
MO-N
is
different
containing
distances
and
distance
more
in
geometry
scheme.
MO
metal
1,4,7-triazacyclononane)
not
the
coordinate
MO-S2
with
Rather
for
eight
given.
= 1.952(3)(av) the
L'MX3
of
(shown
not
determination
in
CL')
by
set
was
complexes
facCaZ
a
structure
MO-p0
the
MO no
tetramethylthiuramdisulphide
product
Mo(S2)(dtc)3
prepared
shown
form
As
by but
and
[1211.
showed
set S4
or
reduced
CompLezes wiS-zn
A
and
with
W(VI)
2.496(2)-2.553(2),
been
MO
reduced
prepared
other
studied complex,
either
suggested
one
partially
[1223.
stereochemistry
z .2.4
sets, the
reacts
to
been
MO(V)
determination
two and
the
been
A structural
toluene.
contrast
In
has
the
from
was
oxidized,
have
for
form
interaction
MO-S
with
oxidase
found
oxidized
[Mo(Et2dtc)4113 in
arsenite
unaltered.
a MO-S-AS
and
of
example
understood
(P
which = PMe2Ph,
adds C1241.
to
the
less the do
71
LMo(co13
1
LMo/o>M*L
and
ITo 0
II 0
q.pa-
yellow 2+
(52)
+2H+
-2EI+
H2°
LW02Br2
I I LW-o-WL
)
I \I 00
I
2+
0 00
HN03
Lw(co)j
Br2
I [LWOBr2]Br
0 LW< >wL II O II 0 0
H20
I
H20,Zn/H+
green
argon
solution
I
O2
L I 0L;/“\i
[
‘0’
y-0
I 4+
*
I
2+
0
L$.o.wL
O2
[
(53)
.O/
1 2+
II 0
Reaction 180°C
gave
square the
of
Mo(C0)6
phthalodinitrile
oxophthalocyanato
pyramidal
0x0
with
MO(V).
geometry
group_
Bond
with
the
distances
are
A MO
in
crystal atom
Mo=O
toluene
structure
0.69%
out
= l-668(6)
in
a
sealed
tube
determination of
and
the
MO-N
N4
at
showed
plane
a
towards
= 2.068(6)-2.112(7)%
c1253.
2.3
MOLYBDENUM(IV)
2.3.1
HaZides
AND
and
ha20
Interaction (norbornene, A
theoretical
been
in
early
transition
by
a
of
of on
interaction
disulphide
confirmed
or
WC16
with
gave
crystals
the
carried
terms
conclusions
The
The
MoC15
study
has
symmetry
=3h general
compZexes
cyclooctadiene)
[Mo~S~C~~]~-
the
of
TUNGSTEN(IV)
a
out
role
metals
+
bridge
was
0
and
of
in of
the
presence
B-electron
it
explains
and
treatment
capping
ligands
2SH
and
MoC15
dichloromethane
(S2P
is
from
idealized
leads in
gave
CC13~~(~2)C12~~C1312-
-
identified
crystallographic
in
by
study
IR
and
+
spectroscopy the
to
some
clusters
of
is
the
reaction
2~~1
(vS_~
structure
= 609cm
shown
in
-1
> and
(54)_
2-
(54)
\,I
Cl
If
cluster
distortion
The
Cl/ ycly distances
olefin
[1261_
,fl\ Mo/iAMo/y, Bond
an
(MO 111)2M01V
the
distortion_
bridging
of
MC14(Et20)2
c1271.
NEt4SH
(MoC$)~
2
trinuclear
Jahn-Teller
the
of
Et
are
MO-MO
=
2.763(2)
MO-Cl
=
2.393(3)-2.416(3)
regarded
as
a
single
MO-S
ligand
MO-uC1
the
geometry
=
2.435(4)
= 2.468(3)%
of
the
molecule
is
almost
73
ideal
for
single
two
bond
electron
2.3.2
face
and
with
g5Mo
The
of
nature
NMR
They
recorded_
the of
on
spectra
of
are
donor
atom
donor
a
a very
signals
magnetic
metal
oxygen
cover
the
the
each
properties
is are
consistent
with
consistent
with
a one
11281.
large
number
range
extremely the
of
of
Mo(IV)
chemical The
broad.
on
distance
ligands
wide
ligands
MO-MO
The
octahedra_
interestingly
localized
Complexes
some
sharing
complexes
shift
effects
linewidths
and
have
(61035
of
to
been 63180)
and
stereochemistry
and
shifts
discussed
chemical
are
the
c1291, Blue
diamagnetic
compound mole
to
reported
equivalents
showed
it
of
168O_
of
the
more
to
of
The
excess
corrected
rate
the
is
product
thiocyante
been
that as
rate
four
follows:
was
at
1
also
of
oxygen
H20(tra?zs
u20)
a
structure
about
remaining
water
complexes
containing
is
k
the
isotopic
of
the
same
as
in
CNCSI-
to
molybdenum 1,911 (w
and
111)2W1v
shown
in
2M
HCl
give
90°C
=
cluster
with
2.11Og_ like
arrangement %Pr
their
and
it
is
to
amount The
1'
With
statistically
sites
a small l+k
a
studied_
give
of
the
CNCSI-,
aquation
of
the
with
3yrs,
gave 2+
11321,
water
techniques.
molecules
was
It
rates
H20(trans
oxalate
p3 -0
solvent
with
u30)
found
half
about
l_lh
confirmed
Others
cases
and and
[Mo~O~(OX)~(H~O)~~*salt
have
that
prepared
the
the two
Cs3[Mo304(o~)3(H20>3~_CF3S03.3H20 all
lives
and
structure
of
the
anion
c1331.
followed
bond
the
been
and
different
CPt(enj21
to
anion,
(55)
44
very
>
In
[W30,(NCS),15-
analogue W-N
at
four
angles
similarly
equivalent
the
CW3(P3-Ol(lJ2- o),(H20),14+
Orange K2[WC16]
is
to with
have
[NCSI-
With 4+
with
Cs2~Mo304~ox>3(H20)33-4H20.C.3H2C204_ is
eraa-O-W-O
prepared
tracer
at u20
trans
same
with
c1311.
Reaction
was
kltMo304
In [Mo3041
days,
determination
molecule
W(IV)
determination
due
[Mo~O,(NCS>~]~three
=
exchange 5
by
+ k 1_
studi::
oxygen
2omin.
and
sites
was
4+
assuming
/3)[NCS-1
oxygen 18 using 0
about
WC14(SEt2)2
acetylenes
CMo3041
of
25OC
types tJ3
crystal
(k
and
exchange
studied
the
of
used
I
monomeric
structure
1_86g(av)
2,6-C6H3Me2)
first
treating K-ray
coordination
product
[Mo304(%113+
of
=
the
cl301.
the was
=
towards
anation
k
complexes
The has
the
by
W-O
potential (R
is
in
with
unreactive block
constant
constant
prepared
planar
[NCSI',
equilibrium
2,6-C6H3(iPr)2)
was
acetylenes
of of
=
toluene/ether.
W(OR)4
towards
kinetics
large
is
which
analogous
reactive The
it
in
square
compound
The
(R
and
LiOR
almost
phenoxides
groups_
a
he
W(OR),
which
has by was
distances
been
ion
shown W-W
to =
EW304(H20),14+
can
its
analogue
molybdenum
prepared
exchange
be
by
the
separation_ have
the
2.534,
W-u30
reduced
to
(1341.
same = the
hydrolysis It
reacts
structure 2.039,
W-u20
corresponding
of with as =
its
74
H
2
2
Bond
distances
for
the
triflate
The
2.491(l)
MO-~30
=
2-01(l)
MO-0(H20)
=
2.15(l)
MO-U20
=
1.908(2)
MO-0(0x)
=
2.102(8)x
compound
~W302(OAc>6(H20>(OH)2~.16H20
isostructural
between salt
with
water CW
0 32
detected
and
hydroxy
the
shorter
dependent
than upon
W-H20 in
and
evaporation was
characterized
trinuclear each
edge
corners the
the are
crystal
X-ray
with
metal formed
the
6
P 3-O The
by
H-bonding
strong
H302
2
and
disorder
in
of X-ray
OH
KBr,
the
to
crystal
double
diffraction
ligands
almost
found the
as
suggesting
could
short
be
as
that
the
this
W-OH bond
c1351. in
dilute
KCNS
0)(H302)](NCS).H20 The
oxygen
triangle.
is
cation)
(H
diffraction.
two
and and
lattice
dissolved
prepared
atoms groups between
structure
solution
and
crystallized is
the
usual
and
two
acetates
bridging
link
the
clusters
at
OH
on
one
out
cluster
two and
H20
C1361.
Interaction extensive
by
aquo
in
is
presence
H20
distance
tris
was
that
[W302(0Ac)
complex
arrangement of and
other
the
the
crystallizes
bond
the
been
There
in
so
H-bonding
CW~O~(OAC>~(H~O>~~(CF~SO~)~ after
has
analogue. However
groups-
However,
(and is
molybdenum
(H 0)(OH)2].K3r_15H20 6 2 disorder in this crystal
distinguished.
length
its
(OAc) no
distance
are
=
MO-MO
be
complex
workup, structure
of a
and
W(CO14(pip12 low
yield
determination
of
the for
HOAC/acetic
anhydride
bromide
showed
a
after
gave,
cluster.
CW30(CMe)(OAc)6(H20)312+ the
mixture
stereochemistry
A
on
75
similar were
to
those
disordered.
but
may
be
and
one-electron
of
The
W-W to
+2
of
cation
the
Electrochemical pairs
of
amounts
CM0~04(cys)~l led
Individual
of
+l
of
reactants
is
pH
+I
dependent
Th e
cation
is
but
sharp,
fast
the
cluster
is
The
cluster. equilibrium
electron
+l in
The
electrochemically-
subsequent
but
species,
2.801(1)~.
diamagnetic a
observed
slowly
is A
'H
NMR
formation could
of be
is and
all
eLght
separated
consistent the
general
possible by
only
ion with
scheme
exchange initial envisaged
due
at
a
formation [1371.
-0.95V 2in
vs
NHE
of
equimolar 4+ .
[Mo~O~S~_~]
_ The
techniques
of
formation is
of
to
them
in
shown
the (56)
cub ic for
C1381.
CMo3041
0
slowly reversible
spectrum
between
triangulo
groups
paramagnetic,
cation
broadens
exchange
capping
solution.
reduction at a mercury pool electrode 2_2and CMO~O~S~(C~S)~I , CM020~S(cys)~3
products 5+ [Mo~O~S~_~~
compounds pair
the
complexes
distribution
one
to
trinuclear
distance
is is
and
bicapped
the
there
couple
solution
the
other
reduced
re-oxidized
fresh
of
4+
0
II ,
I
O,
MO
MO 'SI
CMo302S21
4+
(~-01
CMo302S21
4+
(Q-S)
‘S’
--+
(56)
CMo3S41
4+
76 2.3.3
Comptexa
with
Addition
suZphur
donor
Zigmds
of MoCl 4 to two mole
equivalents
2,4,6-triisopropylbenzenethiolate) reduced
to Mo(SR>4
crystallography slightly number
which
WC14(SEt2)2 showed
with
it to be
geometry
thiol
tetrathiadecane)
by
an analogous
complex
MoC14(thfj2
and
the
structure
of
oxygen,
but
X-ray
by
the
to be a
forms
a carbonyl
X-ray
is rapidly
molybdenum
compound
prepared
of NEt3_
It
a
adduct
was
interaction
of
crystallography
molybdenum
compound
with
cl.301.
(dttd
= 2,3,8,9-dibenzo-1,4,7,10-
PPh3
formed
+
latter
MoO(dttd)
the
by
+ 20-MeSC6H4SH
the
was
planar
(17)
The
isolated,
corresponding
+ PPh3
was
be
square
Mo02(dttd)
Mo02(dttd)
and
the
and
and about
= 2.262(2)x.
presence
with
is reduced
to moisture
W(SCMe3)4
in the
tetrahedral compound
could
(SR =
MOOCH_
stereochemistry
MO-S
[1391_
isomorphous
Mo(VI)
with
which
isolated
the
between
The
adducts
to be
the
of Me3Si(SR)
surprisingly,
sensitive
showed
tetrahedron
of acetylene
too unstable
is very
on Mo(SR)4
flattened
gave,
+HO
compound
+ PPh30
reaction
MoO(MeSC6H4S)2
-
2
was
determined
and
is shown
in (57).
0
(57)
Similarly tridecane compound
the pentadentate (H2L) MoOL,
Reaction
reacted whose
an
are
MO-P
interesting
is thought
that
MoC14(thf)2
in the
is shown
in (58)
and
with
the
MeCN)
with
structure
the phosphorus
= 2_472(10)(av)
contrast S-S
with
enzo-1,4,7,10,13_pentathia-
2,3,11,12-dib
(L = PPh3,
compounds
to be octahedral
distances
with
structure
of MC14L2
MEPhP(CH2CH2S>212 shown
ligand
and
MO-S
MoCS(CH~CH~S)~I~
interactions
tend
presence
of water
PPh(CH2CH2SH)2 of
atoms
the
gave
the molybdenum C&T
to each
which the
was
Bond
The
compound
is
prismatic,
It
is trigonal latter
compound
other-
= 2_348(12)~(av).
to favour
to give
c411.
and
the
introduction
77
of
the
two
favour
of Two
phosphorus octahedral
new
structures
the
bmpd-
former
with
n
series
= 2)
while ligand,s
series
there
are
structures Reaction
each
nitrogen the
nta
feature u2-s
dmf
of
the
are
gave
six
the
second
give and
ligand
shown
compounds
and
two
(se-613
mpd-
(60)
the
only on
basis with
nta
carboxylate
of
reaction
be
the
five
balance
For
the
of
their
conversion
the
in
36OMHz
the
were 'H
stoichiometry
In in
NMR
crystals
the the
to
one of
trianion
the
original
first second
isolated
and
spectra
cl401.
acid
(H3nta)
of
consists
purposes
the of
and
(61)
nitrilotriacetic
structure
the
types
isolated
the
while
compounds
workup)
in
of
and
compounds.
coordinated
present
W(IV)
for
chelation
excess
The
oxygens. to is
the
.
All
protracted
ligands
of
prepared
stereoisomers
gave
rings.
(after
assumed
tips
mpic-
rings
S),(nta)(ntaH>,l.
is
this
on
been
in
(two
series
5 membered
tridentate
sphere
complexes
have
4 membered
afforded
ligands
c1411.
chelate
(NH4)2[Mo3S13j.2H20
(NH4)3[Mo3(u3-S)(~2with
mixed
determined of
refluxing
4
coordination
[gOI.
(59)
both
in
the
W(bmpd)x(mpic)4_x
ligands
series
their
of
and
of
into
geometry
series
W(bmpd)x(mpd)4_x
The
atoms
of
the
Mo3S4
molybdenum charge
form.
balance The
IJ~-(S~)
core
through one
interesting group
to
of
78 Electrochemical -O_85V ion On
vs
NHE
at
exchange
a mercury
separation
addition
The
reduction
of
structures
pool
Na2[Mo202S2(cys)2]
electrode
procedures,
CNCSI-
they
of
cations
the
gave
gave
gave the
are
in a
green
given
4+
and
[Mo~S,(NCS)~]~in
(621
and
HCl
under
solution
[~03~4(~20)91
known
2M
at
which,
after
CMO~S~(H~O)~~I~+_
and
(63)
H2
cMo4S4(NCS)12]7-.
E1421.
I’
I MO/S\
\
of
‘l\/y
s\I/s
‘I’
(62)
MO
(63)
‘I’ Reaction hydrolysis and
a
and
second
identical provided whose was
by
shown
grossly
the
to
be
2.3.4
acetic
whose
visible
(I).
isolation
of
was
determined
due
to
the
change which
is
the
with
of
investigated.
All
stoichiometry
of
4-MeC6H40H
Mo(NMe2)4
the and
and
with
products
to
be
geometry
of
this
products
coordinate
similar of
4+
(I)
but
not
[Mo3S41 to,
was
[Mo3S414+
band
structure
[144].
The
of
(II)
the
structure
is
a
and
the of
publication, and
2.791(l) to
to
by
Cs2[Mo3S4(ox>3(H20>3].3H20
reported
presence
2.869(1)?~. It was 4+ by air oxidation [Mo,S,]
coordinating
ligands
(such
as
donor 2 igands
phosphorus
series
alkylated
of
paramagnetic
depended
2-tBu,6-MeC6H30H
were
identity
isolation
=
due
followed
cl441.
a
3,5-Me2C6H30H
five and
the
were
trans. Mo(OAr)4(HNMe2)
presumed
2,6-zPr2C6H30H
in
spectra
the
reflux
bands
subsequent
converted
trimer
nitrogen
the
MO-MO
slowly
the
a
was
with
accelerated
stabilize
CO?RpZexces
Reactions
type
WV
complex In
under
green
of
oxolato
[1431_ 6+ and
[Mo4S43
is
and
Confirmation
of
cubane 6+ [Mo4S41
anhydride
yielded
(NH~>~EMO~S~(NCS>~~I_~OH~O
that
the
oxalate)
and
separation
(II)
that
distorted
observed
With
exchange
product
structure
Na2S
Mo(COj6,
ion
with,
derivative
and
of
upon
the
species gave
were
obtained is
not
phenols
have
been
= l-10-1.79BM)
steric
the
products was
(u
demands
but of
the
Mo(OAr)4(NMe2)2 with
known.
The
alkoxide.
which
2,6-Me2C6H30H
Mo(OAr>3(NMe2)(HNMe2)
the
sterically [1451.
but
were the
demanding
79
cwp&q in
scheme
(L A
(63).
indicated Bond
4+
in
the
distances
=
1,4,7-trlazacyclononane)
crystal scheme
are
=
[92]_
The
N,N',N"-
compounds
of
the
type
crystallographic distances
MO-N
The
tridentate W-u30
by
confirmed
of
as
confirmed
coordinated =
also
=
with
in
of
manner. W-N
and
gave
L'MoBr3.
2_365(4>-2_458(3>%
=
Mo(IV)
A the
ligand.
1931.
Bond
Stmilar
C941.
N,N-bis(5-*
(64)
1.94
(L') of
earlier
structure
a facial
W-u20
oxidation
=
indicated
the
in
2.10(av),
fffcidcoordination
Mo-Br prepared
W(CO>6
(H2-L2-Lv2)
mild
the
2.237(13),
were
reaction
diaminobenzene
determination
2_52(av),
[L'MoBr31+
=
complexes
the
isolated
trimethyl-1,4,7-triazacyclononane
study
are
tungsten
with
W-W
2_14(3)-Z-26(3)2 ligand
structure
was
dry
Bu-2-hydroxybenzylidene)-1,2-
mesitylene
Me
at
170°C
gave
a very
complex
Me
(64)
mixture four
of
more
species
than
have
coordinate
W(L2-LU2)2.
identical,
but
signals
indicating
a
of
WH5(PMe3)3M'_ ether
determined. the of
the but
potassium
hydrides
are
two
are
extreme
of
H
IR
spectra
5
case the
salt
of
directed of
for
of
which towards the
of
are
achieved
of
the
the
four
different_
by
TLC
neutral
isomers All
are
showed
with
no
Inherent
symmetry
or KH
in
thf
yellow
and
eight almost bl3U
four
and
possible
[146]_ NaH
X-ray
> M'(crown) 33 the sodium
geometry for
spectra
complexes
was
stereoisomers
NMR
with
(PMe
separation
as
and
suitable WH
views
Partial
discussed
Crystals
In
the
set
WH6(PMe3j3
adducts
analysis, the
36OMHz
were
Reaction
species_ characterized Visible 1
their
stereochemistries
crown
15
been
the
all
diffraction and
salt,
bonding
structures
the
hydrides
as
shown
in
two (66)
prepared of
was
Ligands
and
compounds
and
not
(66)
were
detected
observed.
from
the
adducts
identical
were
away
for
both
were
fragment
hydride
potassium
were
the
W(PMe3j3
the
gave
potassium_ [147].
to
in that
Three There
of
80
_ PMe3
PMe3
“,,,\
0
1 /H -
-
along
the
analysis
lithium
simiLar
to
that
of
A
crystal
the
terminal
Me
from
tungsten of
the
Na
nBuLi
square long
hydride and
and
K
gave of
(66)
and
the
[WH5(PMe3)8Lil4
tungsten
short
ligands,
atoms
Li-W
it
is
arrangement
salts
WC14(PMe3)5
structure
feature
the
tungsten
in
excess
a
alternating
between
solution
HH/i\HH/K
and
contains
reveal and
Reaction addition
with
not
between
yellow
WH6(PMe3j3
showed
edges
6
\
(4351
between
did
I /” --
PMe3
PMe3
crystallography
Me3P\
0
'0'
HH
Reaction
1
b
K+
HH /;\
0
/
which having
distances. possible
of
the
X-ray
lithium Although some
that
the bridge
fragments
W(PMe5)8
LiAlH4
in
Et20
at
-8OOC
followed
by
NCH CH NMe 2 yielded insoluble Me2NCH2CH2NMe2A1H3 2 2 2 which was isolated (PMe3>3H3W(~-H>2A1(H)(~-H)2tJH3(PMe3)3.
hydrides structure
resolved
were is
not
H
W’
the
clearly
bridging
the
is
11471.
and
determination
atoms
resolved. section
H\
.Al’
‘“‘I
hydrides
attached The
shown
to
most
in
Al,
a
but
the
interesting
(67).
,w
and
The
complex
(67)
\H H
can to
be
considered
describe
it
as as
[AlH5]
fluxional
in
solution
-8OOC
at
this
the
and solid
state
Reaction addition
of
at
with
between CsCl
2-
gave
brfdging
room
temperature structure
CompZexes
2.3.5
a bis-WH4(PMe3)5
adduct two
temperature 1 the H and
of
but
AlH8,
[WH3(PMe3)3]+ but
rigid
31 P NMR
it
on
the
equally
The
units.
spectra
is
NMR
are
valid
compound
is
timescale
consistent
at with
C1481.
mekat-carbon
bonds
NaK3[Mo02(CN)41_6H20
and
Cs2Na[MoO(N3)(CN)41-
A
NaN8
at
pH
crystallographic
9.5-10
followed
study
showed
by a
81 trans
configuration
displaced
N3
ligand
121(61°
is
the are
distorted plane
MO-O
but
linear,
field
KCN by
tungsten
at
the
the
photolysis
the
four
= 1.70(l),
angle
the
interaction
complex
at
anion
cyano
MO-N
with
groups
the MO
towards
= 2.29(2),
MO-C
the nitrogen
bound
alkaline
solutions
atom the
of
presence intensity.
NMR
have
species.
the
signal
given
The
= 2.17(1)x.
to molybdenum
is
structure
of K4EM(CN)81
the pentacyano
MO,
and
complex
but
cyanide,
due
of
on K~CMOH(CN)~I. as
appearing
spectra
a doublet
solutions
that
the
+ OH-
and
The the
not
also
the
but
addition
also
is fluxional signal
showed
of base
determination
reduced
with
KCN
showed
gives
CMO
--L
K5cMo3S4(CN>g].3KCN.4R20
a typical
Nc\
Mo(IV)
trimer
core
and as
a crystal
shown
I /CN
5-
MO
S’I ‘s NC\I /\I /CN Nc~io'S~~~CN CN
CN
are
MO-u3S
its
equilibrium
CN
MO-MO
appears
the
C1511-
of MoS3
distances
was
for
molecule hydride
of K5[Mo(CN)71
to the hydride,
is suggested
in solution
Reaction
For
CMOO(OR)(CN)~I~-
been
spectrum
I3 C NMK
It
of
aqueous
EMOH(CN)~I~-
Bond
0x0
ClSOl-
details
The
82.3.
of
q CMO(CN)~~~-
gave
Further -t_ the l'C
occurs
of
octahedral
11491.
containg
with
of
distances
Ligand
formed
out
0.282
Bond
group.
for
= 2_775(ll)(av) = 2.363(3)
MO-C Mo-u2S
= 2.182(13)-2.222(10) = 2.312(2)-2.324(2)g
(68>
in <88)_
82 The
crystal
paper
Bond
IR,
and
the
The
;*\
S
2_758(7)
=
2.06(5)-2_22(5)2
resonance
the
Raman
anion.
of
former
as
Bond H)
The
also in
iN,
reported
of MO-Cl 3-
=
been
were
8-
CN
to
this =
be
presented
and
active
complex
together
olefin
2.439(2)-2_469(2)A
in
(H 0
the
73 case
)(NMe in
MO-MO
=
and
other
Mo-Br
(NBu4)2[Mo2Br6] the
2.384(4), =
with
course
+
PEt2Ph,
a
detailed
of
the
-
2L
PEt3
or
1/2dppe.
have
epoxidation.
the
A
been crystal
octahedral
Br
8
HI
does
not
structural Mo-uBr
=
2_546x(av)
monodentate
disorder
studies
on
is
addition,
salts
2.630(av),
bidentate as
in
scheme
(70)
(NBu4)cMo2Br5L41
In
in
[154]. and
reactions
show
(NBu)[Mo2Br5L21
-
Mo2Br4L4
PEtPh2,
with
[153].
)CMo
4 2 previous
are
and
2.295(14)
(dppeH2)3[Mo2C1912
in
confirmed
2.635(5) of
=
c1521.
distances
investigated
=
same
(69).
12L
L
the
'CN
(dppeH2)3[MoC1612
(NBu4)2EMo2Br61
where
in
TUNGSTEN(II1)
proved
has
reactions
been
shown
/\*
spectra
AND
[Mo2Br8H1
state
Mo-Br(trans
is
,
CMO~S~(CN)~~I
for
with
anion
solid
anion
MO-S
=
MO-C
determination
The
have
,,/
MO-MO
stereochemistry
this
S
preparations and
structure
the
iN,
analysis
reported
the
NC,
MOLYBDENUM(II1)
2.4
of
was
are
and
vibrational
(PPh4>2CMo2S2(CN)8]_nH20
stereochemistry
distances
Raman
of
structure
the
reaction
phosphines (70).
of
83 (NBu4)[Mo2Brg(dppe)21
was
reported
was
determined
in acetone and
distances
are
2_532(8)2
[1551_
Trans very
structure
MoC13(thf)3. CMoC14py21-
MoC13(thfj3
were
of
(ttt)
The
basis
formed The
readily
complexes
and
isolated
MoC13(ttt). the
are
IR studies,
in reactions
reaction
distances
will
probably
of
other
prove
Mo(III)
stereochemistry
is more
Bond
P> = 2.565(4),
stable
[MoC14(dppe)]-,
was
MO-P
to be
=
a
complexes.
with
MO-Cl
in solution
A
=
than
[MoC14(PMe2Ph)21-
and
W-W
prepared
by
the
and
involved
WC14(SMe212
mixed
cleavage and
Addition
determined
(hto).
by X-ray
excess
of PPh,Cl
of
le\
structures oxidation
were
state
the macrocyclic
Et3SiH gave
diffraction
Among
MoCL3(ttt)(thf)
polymeric
some
of
1,4,8,11-tetrathiacyclo-
(MoC13)2(hto)(thf>,
insoluble
interaction
gave the
and
the
and proposed
compounds ring
51571.
diamagnetic
chloro
is shown
derivative in c71)_
7 <71)
are
H) w-s
hydride
been
polythiaethers
In addition,
which
between
w-cl(trans
The
the It
have
the
MoCl3(hto),
complexes
of
structure
the
and
(NBu4)[MoBr4(dppe)l
geometry-
1,4,7,10,13,16-hexathiacyclooctadecane
were
w-w
of
to give
of
Mo-Br(cis
preparation
confirmed
with
Cl
Bond
the
of Mo(II1)
C13W(u-H>(u-SMe2>2WC12(SMe2). whose
structure octahedral
prepared
= 2.154(12)2.
or MoC13(PrCN)3
tetradecane
on
for
+
[1561-
series
complexes
h as been
MO-O
It reacts
crystal
a distorted
P> = 2_586(4)(av),
material
and
(NBu4)[MoBr4(dppe)l
The
has
determination
2.421(91-2.442(8)
A
anion
Mo-Br(tras
starting
-
solution.
the
-CMoC14(thf)21-
useful
crystal
+ 2NBu4Br
bond
= 2.419(l) = 2_407(5),
W-H 2.435(5)
= 1.48
W-Cl
= 2.375(5)-2.394(4)
- 2,372(5)-2,389(4)x
length
is consistent
is noticable
in the W-Cl
with bond
a triple
bond
distances_
and
The
the wms
hydride
NMR
effect signal
occurs
at the very
interesting rotomeric
variation forms
Crystals mixture the
high
of
of
frequency
with
the
at room
which
temperature
is discussed
and
shows
in terms
of various
Cl581.
(NMe4>[{MoC1Br(02CH))301
shown
is
temperature
anion
of MoBr 3, NMe&Br
anion
of 63.71
and
HCOOH
were
in EtOH
isolated
saturated
from
with
the
HCl.
reaction
The
structure
of
in (72).
Cl
I/ \
0 \
/
MO
‘C
I \
/ B?-
(72)
0
0
\ Cl/ \B/
Bond
distances
electrons and
the
spectra
structure
= 2.&?o(av) = 2.53l%(av)
is similar
to that
of
the
but
formal
oxidation
available
for metal-metal
bonding.
study
The of
distance has
spectra the
the
been
first
is retained
is consistent made
suggested
=
on reduction
state This with
(MO =v> 3,
of that
two were
Mo(IV)
the
almost of
is 3.33, suggests
this
species
identical
(MO Iv13
trimmers with
(MoI1113
latter
1.976(3)
- 2.080(4)-2.098(4)
MO-O
triangle,
A Raman
the
MO-&I3O
Mo-Br
internuclear
solution.
‘Cl
= 2.596(l)
MO-Cl
structure
the metal
/
are
MO-MO
The
I
MO
so there a bond
capping
are
order
eight of
1.33
fl591. and
(MoI")~
has
suggesting
c1601.
a u3-0
a p2-0x0 that
in aqueous bridge the
and
trimerlc
85 Interaction MeOH
in the
isolated
of Mo(NNHPh)2(butane-2,3-diolate)2.H2NNHPh
presence
black
determination
of NEt3
crystals
of
revealed
gave
a deep
purple
solution
(NHEt3>[Mo2(NNPh>4(SPh)53'
the
arrangement
shown
with from
excess
which
A crystal
HSPh
in
were
structure
in (73).
Ph -N
‘“\ /%I\ ph’N-N /Mo \‘/
SPh
N-N-
MO -
S Ph
PhS
Bond
distances
= 3.527(l)
Mo-pSPh
= 2.533(5)-2.653(5)
MO-N
probably
very due
distorted
long
MO-MO
to the
electron
of PPh3 shown
the usual
manner
addition
of
from
CS2
yield
formed
aqueous
mtZ-tL2M02041 the
terminal
confirming LMo(COj3
groups. of
bond
The
reaction
ligands of
the u-n
interaction
ligand
contains [162].
mechanism
of
remain
original 2
between
ligands
the metals.
and
CS
a free
C=S
unit
the reaction
and
(formed which
of green
(L = 1,4,7-triazacyclononane)
oxygen Br2
atoms atom
in the
transfer
in CHC13
gave
product C1631.
are With
monomeric
derived the
same
CLMoOBr2]Br.
in the the
chelating
is modified The by was
is
11611.
has
are
is
unit
CS2
which
of CS2
this
distance with
intact dtc
and
Mo2(SPhj3
the MO-MO
C2S3
in by
ligand
S abstraction methylated
to
diamagnetic with
solution have been investigated. The reaction 2+ 18 quantitatively. By use of 0 enriched N03oxygen
with
dtc
cation
CL(H20)M~(0H)2M~(H20)L14+ acidic
NNPh
extraordinary
is bound
the
This
and
an
fourth
which
corresponding kinetics
Three
the
by
a metal-metal
lengthening
Z-525(5)
= 1.26(2)-l-37(2)8
Mo2(dtc)3(p-CSC(S>S)(~-S3C2NEt2)
(74).
while
by PPh3).
the The
to give
a CS unit
is presumably
the
undergoes
in
precludes
withdrawing of
= 2.449(7),
N-N
distance
aa a consequence
structure
Mo-SPh
= 1.73(1)-1.83(l)
Mo(C0)2(Et2dtc)2 presence
\ N -Ph
are
MO-MO
The
(73) N
from
the
ligand,
nitrate
ion
in
yields it was
shown
nitrate, oxidation
Reduction
of
that
thus of
this
in
86
NEt2 /
s
--A / Mo2 I \
S
Bond
distances
aqueous
(74)
S
are
solution
MO-MO
= 2.616(l)
MO-C1
= l-920(9)
Mo1-C3
= Z-026(8)
Mo2-C3
= 2_086(9)
Mel-S4
= 2_449(3)
Mo2-S4
= 2.406(3)2
by
Zn under
4H20
[Mo2L2(V-OH>(U-Br>Br21Br2. CMo2L2(W-OH>2Br21.2H20.
N 2 followed
The
whilst
structure
by
addition
reduction of
the
of NaBr
at elevated
former
was
gave temperatures
determined
and
gave ie shown
in (75).
-r \ (/ N
N
Bond
distances
The
N
I/ I’
Br
H
MO
(75)
/ Br
are
MO-MO
= 2.558(3)
MO-N
Mo-Er
= 2.547(7)
Mo-uBr
MO-POH
= 1.84(2)x
short
MO-MO
separation
indicates
strong
= 2_19(3)(av) = 2.558(5)
bonding
and
a triple
bond
is
87 suggested
The
c1641.
similar
with
bond
and W-N
= 2.2O%(av)
Reactions
structure
distances
of
W-W
= 2.477(3),
of W(N2)2(dppe)2
[W(OH)(NNCMe2>(dppe>2]PF6
with
in dichloromethane
study
EBFI-
2.312(5)
2.5
and W-P
retain
the
a different reacted
that room
the
with
tetrameric
On
n. cluster
re-generates which
product
to
basis
of
[Mo2Br61 2- has 1,2-dibromoethane.
The
on faster at room
are
2/3
rates
temperature
but
(PPh
their
B-MoC12
(PR3
Br\ I /
supports the
two the
Br
C1C6H5
[166].
W-Cl
=
Direct
to
Mo(CO>~ and
gave
AlC13
A spectroscopic
reaction
suggested
with
PR3
at
and
NEt4Br
t1671.
of Mo(CO)6
electrochemical
appear
reaction
Mo4C18(PR3)4
view
interaction
with
S-MoC12.
clusters
the
these and
Mo2(OAc)4
of
this
second
gave
studies
reaction
oxidations.
is irreversible
and
(PPh3Mej2S6 l/3
gave
The
under
in
first
all
mixed
single
is
scan
crystals
(PPh3Me)2[Mo2Br6S2(NO)21
Br
,,\ I /- No
ON/;‘\BrAi ’
1
with
= PEt3,PCPr)3,
precursors
form
clusters.
Me) [MO Br (NO) ] and 3226 4 in (76) and (77) [66].
NO
r
a crystallographic
cl681.
of Mo(N0)2Br2
shown
of
rectangular
by
shows
gave
with
geometry
spectroscopic
a reactive
the
prepared
anion
scan
interaction
of containing structures
been The
and kms
Prolonged
to be
give
with
of W(N2)2(dppe)2
Mo~C~~(PR~)~
arrangement
appeared
product
in refluxing
Mo~CI~(PR~)~.
C1C6H5
this
the
solution
to have
or MOM
also contains tetrameric 2 temperature to give Mo4Clg(PR3)4
conditions
= 2.545(5)
C1651.
6-MoCL
reversible
to be very W-Br
in H20/thf
CWC12(dppe)21+
clusters
MOSCOW
product
of
found
a condensation
Reactions
cation
TUNGSTEN(I1)
in refluxing
comparison
the
AND
rectangular
phosphine
gave
showed
2.563(5)x
E~Io~C~~(PR~)~I
products
isolated.
= 2.522(5),
of
P(nBU),,PMe2Ph)
with
salt
MOLYBDENUM(I1)
Reactions
was
= 2.095(20),
HFeCo3(C0)12
In acetone,
was
HFeCo3(C0)12 the
W-pOH
[923.
[W(OH>(NNH2>(dppe>2][FeCo3(CO)~2].
on
2+
[W2L2(p-OH)2Br21
NO
2-
(76)
Br
whose
88
(77)
L
Bond
distances
are
= 3.978
MO
MO...
=
2.590(av)
MO-N
=
1.837(12$
Electrochemical
studies
CMo(H3{Me2pz}~(NO)12]-
which
which
a
itself
undergoes
Reaction
between and
CM(C0)2(tipt)31X-ray
diffraction
bipyramidal
of
MO-S it
species,
corresponding
other the
reactive
and
and
NNPh
Mo-N(MeCN)
=
2.6
to
PMe2Ph
2.227(14),
series
of
(P-P-P
=
be
two
mole
The
have
equivalents
structures
tridentate either
of
ligand NH3
=
or
also
N-N
products.
showed
distances
are
a
formally
of
could
whilst
be
trigonal
MO-C
CO
=
gave
the
easily
[NNPhlC
in
MeCN
confirming
Mo-N(NNPh)
1.211%
a
14-electron
Addition
are =
gave
similar
determined,
distances and
gave
carbonyl ligand
was
Bond
for
extra
of
C1691.
complex
addition.
carbonyl
2.32(av)
complexes prepared
under PMe2Ph
the
compounds
was
usually
N2H4
the
formation
=
gave the
l-782(12),
[1701.
TUNGSTEN(O)
been
of
Bond
expected
structure
axial.
thiols
axial.
the
2,4,6-%3C6H2SH)
molybdenum
and
but
mono(dinitrogen)
PhP(CH2CH2PPh2j2)
(Htipt
the
.
Mo(HBCMe2pz}3(NO)I(solv)
=
As
MO-S
AND
Mo(N2)(P-P-P)(L-L)
gave
to
form
Htipt
of
one
to
oxidation
substitution
whose
ligands
I-
carbonyls
replace
2_662(av)
showed
demanding
salt
anion,
MOLYBDENUM(O)
A
loses
and
the
2.396(15)
=
one-electron
aterically
with
[Mo(MeCN>(NNPh>(tipt>33MeCN
slowly
PPh4+
=
Mo(HBiMe2pz)3)(NO)12
reversible
tricarbonyl
NCR
removed.
Mo-pBr)
2_317(5)-2.342(5$.
=
is
on
McCO)4Br2
structure
1.96(av),
Mo=S
Mo-Br
c1711.
by
limited or
one
were bound
Mo(N2)(P-P-P)(PMe2Ph>2 Na/Hg
mole
of
determined in
reduction
amounts
a facial
of
L-L by
of
nitrogen
(L-L 31
manner.
=
or MoC13(P-P-P) in
the
presence
of
dmpm,dppm,dppe,diars).
P NMR
studies
Reaction
and with
the acids
HX
89 Reaction
of
WC14(PMe3)3
> (PMe > which reacted 22 34 X-ray diffraction W(N2)(PMe3)5_
with
Cis-W(N
2_04(2), by
W-P(tzwzs
both
N)
complexes
to
a Na
with
give
further
of
the
2.473(4),
=
dispersion
carbonyl
PMe3
latter
other
under
gave
W-P
and
in thf under
=
Ar
bond
at
40-50°C
distances
2_444(7)s(av)_
acetylene
N2,gave to
W-N
Various
derivatives
were
give
= reactions
described
[172]_ The
complexes
cis-W(N2)2(dppm)2
prepared
by
reduction
presence
of
the
also
reported_
2,481(l),
of
phosphine. Bond
N-N
=
The
trans-W(N2)2(Ph2PCH=CHPPh2)2
WC14(Ph2PCH=CHPPh2)2
crystal are
1_123(4)S\(av)
structure
W-N
=
of
1_983(3),
Mg
in
thf
in
the
cis-W(N2)2(PMe2Ph)4
2.015(3),
W-P
=
was 2.444(l)-
have
and
been
recorded
assignments
over
made
for
a wide
the
temperature
lowest
lying
range
excited
C17741. The
single
diastereoisomer
tmns-M(N2)2(S,S-chiraphos)2
(-)(2S,3S)-bis(diphenylphosphFno)butane) form
by
were
[173]_
data
tirans-M(N2)2(dppe)2
states
or
distances
Photoluminescence for
WC16
and
reacted
MoBr(NNCH(Me)C6H13)(S,S-chiraphos)
enantiomer
over
the
other. to
*rans-Mo(N2)2(dppe)2
in
Several
form
with
which
racemic
there
1,4-dihaloalkanes
corresponding
(S,S-chiraphos
was all
cyclic
=
2-bromooctane a
10%
excess
reacted
to of
one
with
dihydrazido(2-)
complexes
c1751.
2.7
METAL-METAL
2.7.1
Tr
Two
and of
bonded
reviews
One
year.
Cl761
compares the
triple
their
bonds The
As
metal-based only
two
valence other as
with
those
of
in
M2(0Rj6
the
triple
in
bond
spectrum
The
The the seems
close
on
triply
have
bonded metal
to
band
this
appeared
dimeric
oxides.
in
alkoxide The
compounds
one
CEC,
the
last
compounds
other
with
distance
a
and
not the
the
x
complexes due
turn
is EN
review and
overlap outer
ionization
as o
ns
might
CEO
and
and
not
much
I
bond
distance
a weak close
npz this
contact
its
higher
of
between orbitals repulsion
expected_
that
been
and
repulsion
be
so
the
the
reduces
Level
d
only
in
and
core
electron
increase valence
that
lie
have
the
implies
result
G
to
suggesting in
the
valence
does
to
sharp
substantial
destabilize
proximity
Is
M2(0R)6
observed
which
metal of
of
are
unexpected
causes
Lonization M-M
u
a number
bands
ionization, of
which of
of two
before,
origins
orbital
occurs
chemistry
structures
slightly
ndz2
also
of
of
noticed
atoms
a result
area
c1771.
metal
effect
this
review
of
The
metal.
of
and tungsten(.Tll)
a general
ionizations_
interactionthe
aspects
photoelectric
reported_
changes
species of moZybdenmIIIII
on is
reactions
SPECIES
BONDED
the of
the and
This
ionization as
previously
predicted.
species
Thus
may
the
also
A disagreement has
been
and
structures Also,
of both
of py.
described
compounds
of
X-ray
analogue
been
from
quadruply
existence
does
. of W2(OzPr)6py2(p-CO)
exist,
reported
but
before
W~(O'BII)~
and
and
and
CO with
isostructural
dimeric
bonded
C1781.
with
in
solution
is
it
and
py_
The
are
now
confirmed.
or without
the
the previously
[179].
with
W2(Ot-Bu)6
diffraction
the
to CW2(OzPr>,py(u-CO)12
have
is formed
on the
compound
It is isomorphous
molybdenum
ReactFon
BuOH.
the
converted
in
o ionization
literature
appears
W~(O'BU)~(~-CO)
presence
t
It
irreversibly
ionization
to the
in the
resolved.
rapidly
sharp
'extra'
be assigned
pivalic
showed
the
acid
(tBuCOOH)
structure
in
gave
(78) with
W2(02CrB~)~ five
and
oxygens
in
(78)
Bond
distances
are
w-w =
2.2922(8)
W-Occhelate
piv)
= 2.138(7)-2.164(7)
W-O(monod.
piv)
= 2.072(7)8
W -.. 0 = 2.53(av)
eclipsed metals is
and
two
similar
temperature the
both
of
to
are
that
to
the
rigid
monodentate
complete
ligand is
exchange not
metal
the
metal
except
W-W
rapid
bond.
mixture
as the
bridging
Two
each.
is
In
of
of W2(02CtBu)6
but
and
atoms.
there
W2(02CNMe2)6
structures
are
one
and
as an equLlibrium
isomers
isomers
of
tungsten
but
ligand
across
betyween
the
chelated
this
trans
state
solid
the
monodentate,
oxygen
ligands
about
are
essentially
second is
pentagons
a
the
that
in
and
on
for
each
on
NMR
tlmescale
bridge
metal
most
likely
increases
At
but at
the
At
the structure
bridging
exists
at room
corresponding low
higher
interconversion
80°C
the
pivalate
The
exchange
metal-
even
final between
compound
W2(02CtBu)6
W2(02CNMe2)6.
isomer,
the
position,
this
each
between
interaction
axial
isomers,
occurs the
each
weak
solution
temperature ligands
On
long in
pivalates
[180].
to
temperatures
occurs temperature, between
91 The
comproportionation
(0R13k4EM(0~13
has W3
been
used
compound
for
+ (oR)~Mo
to prepare
showed
reaction
Wj
and
+
W2Mo
its structure
A crystallographic
clusters.
to be very
similar
to that
study
previously
of
the
reported
its molybdenum
analogue Cl811. . and @BuO) of W2(OzPr>6py2
ReacFion
The
W3(CMe)(OzPr)9. synthesized is shown
from
in (79)
isomorphous
('BuO)~WECM~
Bond
distances
= 2_74(l)(av)
w-o
= 1.90-l-93
of 4-MeC6H40H
paramagnetism, signals,
but
although
Mo2(NMc2)6 structure
in the was
obtained
determined. alkoxides
NMe
the
structure
MO-N
distance
of 2.242
this
of NHMe2
shifted. gave
determined.
However,
this
(OAr)
the
2 4 confacial
the NMe 2 groups
gave derivative
the alkoxides i s very
confirms
similar
the
was
acting
acting
The
mainly
a few
reaction blue
crystals
) 22 2 bioctahedral
(NMe
)(HNMe
ligand
is an
as the bridges.
of another
its
were
was
with
terminal
with
but
product
structure
arrangement The
Me
of 3,5-Me2C6H30H
Mo2(0Ar)4(HNMe2)4
whose
as
to that
is a small temperature dependent 1 H NMR spectrum showed four different the
contact
MO
Mo2(NMe2)6
the 4-MeC6H40H with
of 2,601(2)x
and
has
of
arrangement
not
was
with
distance
were
presence
= 2.02-2,062
bond
-_ There
2 despite
they
It also and
the W3 complex
= 2,06(l)
W-u0
or 3,5-Me2C6H30H
and
groups. The MO-MO 3(2.66%). The in CMo2C19] amido
w-c
bioctahedral
bridging
not
of
/OR
W-W
to be a confacial
and
structure
C1821.
(NH2Me2>~Mo2(OAr>,(HNMe2)21
amine
The
Mo2($Prj6_
are
Interaction
shown
solution gave WECMe in hexane/zPrOH 3 was metal complex MopW(CMe)(&Pr)g
mixed and
,,\
also
M3(~3-O)(~3-OR)(~2-O>3(OR)6
two
amine
groups
92
are
-&as
longer
to
the
than
Mo-HNMe2
NMe 2 bridge_
typical
bond
length
corresponding
to
of
1,2-Mo2(0Ar)2(NMe2)4, NMR
spectrum
structure
in
three
types
being
gauche
bond
were
transfer
Me
to
determined
single
type
of
to
type
complex.
of
higher
but
not The
is
known
that
study
of 1
H
the
NMH
between
material
is
with
of
for of
the of
in
usual
Mo2(0Ar)3(NMe2)3
unique
groups
rotation
shows on
about
and
The
ethane-type
each
the
metal
Mo-NMe2
spin-magnetization
shown
the in
and
showed
the
between
isolated been
and
in
solid
state.
of
NMe2
to
and
addition,
small
the
carbon The
Me
and
This solution
of
at
w4
in
this
-20°C,
but
groups
%PrOH
and
the
of
occurred,
(>>6
equivs)
a black
is by
NMR
by
X-ray
butterfly
(80)_
c’
is
[185].
6366.8ppm)
skeleton
ethane
bonds
rigid
amounts
reaction. in
typical
triple
be
groups W2(NMe2j6
M2(0Ar)2(NMe2)4.
2.2198(141x
distal
between
from
the of
for
compound
characterized
carbido
showed length
typical
proxima
types
but
bond
gave
w*
\-
distances
the
2.4139(6)x
the
compounds
compound
MO-MO
reaction
has
groups
M2(NMe2)6
material
the
were which
OZfr
The
w,’
Bond
is
than
give
temperatures
molybdenum
different
W4(H)2(O'Pr)14,
different
2.11%
1,1,2-Mo2(OAr)-,(NMe2>3'
is
that
energies
to
studies
to
crystallography
whilst
coalescence
exchange
product
be
is
to
expected
consistent
starting
major
crystalline
structure
on
the
W4(C)(NMe)(OiPr!12 (12
from
hexane
product
as
Activation
structure-
temperatures exchange
in
the
form
is
distance
of
shorter
C1841.
gauche
similar
at
both
bond
is
2-t Bu,6-Me-C6H30H
crystal
staggered
benzene
and
other.
techniques
Addition A
signal
each
length but
C1831.
Mo2(NMe2)6
rotomeric
bond
(l-90-2.00%),
Mo-MO
2.5
Mo2(0Ar)2(NMe2)4
gauche
the
The
in
Ma-NMe2
lengths
of
with
but of
of
2.26%.
reacts
bridging
bond
order
a bond
2,6-Ph2C6H30H
'H
The
terminal
w3
are
Wl-w3
=
2.799(2)
WI-w4
= 2_814(2)
w2-w3
=
Z-822(1)
w2-w4
= 2_747(2)
w3-w4
=
2.795(Z)
Wl-c
=
1*914(14)
w2-C
=
1.956(15)
w3-c
=
2_251(4)
w4-c
=
2_241(14)8
spectroscopy
type
93
. OZPr O'Pr
All
five
and
the other
groups The
between
edges
per
of
the
butterfly
(spanning
tungsten
compound
are
WZ-W4)
atom
bridged
is the NMe
four
group,
There
are
of
three
them
terminal
C1861.
Mo4(u3-N)2(u2-OZPr)2(O~Pr)10
(tBu013M0EN
by a u2 group.
and
and Mo2(OzPr)6
was
isolated
its structure
is
as
the reaction
from
in
shown
OR OR
OR
M3’\ I /
RO
OR
N3/Mo’ ‘\ \ I
RO
\
OR
iPr
R=
MO’
OR
/+
(81) OR
RO OR
Bond
distances
are
Mel -MO1
’
Mel-N3
The coplanar
and
and
two
species
= 2,918(l)
Mol-N3'
= l-996(2)
Mo2-uOR
= 2-058(2)x
= l-841(2)
Mol-uOR
I 2,139(2)
the
nitride
long
Ho-N
about
bipyramidal
distances
reaction
W3(NE~(OzPr),,-
isomorphous
oxygen
atoms nitrogen
(excluding
corresponding
of
the
bridging
is T shaped, any
MO-MO
to single
alkoxides The
geometry
bonds)
with
double
bonds
W2(0'Pr)6py2
gave
and
two
are
all
about short
[1863.
analogous
structure
and
stereochemistry
is trigonal
respectively The
Mel-MOP
2_034(2)
Mo2-N3'
molybdenum,
molybdenum
I Z-552(1) =
with
the
with
between
X-ray
imido
.
and
W30(OCPr),,
(‘BuO)~EN
and
the
imido
diffraction showed the usual bicapped triangular * OzPr groups being the caps. The compound is
one
but
the W-W
distances
are
longer
at 2.556(2)x(av)
94 0
compared
with
2_541(3)A(av)
not
detected
in
its
presence
[187].
It give
was
reported
nitrogen
been
in
the
X-ray
0x0
The
by
working
at
crystallography
and
it
Although 1 IR and H
for
1984
that
the
anion
of
with
oxygen_
complex.
analysis,
review
and
isolated
the
crystallographic
(OR>2M(PhNC(OR)O>2M(oR)2
through now
the
for
intermediate low
has
PhNCO the
with
temperature.
the
central
core
NMR
Fmido
with
carbamatoester one
has
shown
proton
spectra
reacts
only It
the
confirmed
M2(0Rj6
in
to
bridging
bridging
been
was
PhNCO
has
characterized
by
(82).
Ph OlC-N /
(82)
Bond
distances
the
-
(RO)3W1
=
CMe3
W2(0W3
are
w-w
Reaction
R
\I’
with
=
2.488(l)
Wl-c
=
2.17(l)
W2-C
=
2.24(l)
wl-0
=
2.255(9)
W2-N
=
2.15(l)%
PMe3
structure
gave
very
in
(83).
shown
unstable
which
W2(OtBu)5(PMe3)[v-PhNC(OR)O]
has
OR
I 0
RO’
The
data
set
product
suggests
through
an
/c\N/ph OR
1
I’
OR
PMe3
was
not
good,
that
the
formation
intermediate
of
the
but
same
w-w
OR
= 2.358(2)%.
of
the
type
product
with
The shown
monodentate
isolation in
of may
proceed
instead
of
(82)
PhNCO
C1881. Interaction temperature
gave
of
W2(oZPrJ6py
W2(OSPr)6(py)(p-P2)
2 with
Co which
2
(CO)8(u-P was
3 in hexane 2 characterized by
this
at
room
X-ray
PMe3
95
The
diffraction.
central
pseudotetrahedral
unit
W2P2
is
shown
in
(84).
/s;-e\ /tip;
py\
f&84) ipro/w \ %,/ ”\oi;rpr
iPrO
Bond
distances
-
are
w-P f 2_45(2)(av)
w-w = 2.695(l)
w-PO = l-989(6),
w-o = 1_892(7)-l-932(7)
2.074(7)
P-P = 2.154(4)x
turn
The
structure
are
related
reLationships
that
form
stable
they
to
analogous
to
that
CO~(CO)~(V-P~)
of
and
have
phosphine
ligands
1:l
adducts
the
structure
L-L
(L-L
shown
in
types
in
isolobal
monodentate
dmpm, 1 H
dmpe) and
31 P
react
with
M2C12(NMe2j4
NMR
studies
suggest
P
I
NMe2 /
W
(85)
Cl ‘I
‘I
NMe2
NMe2
the
by
which
(85).
I
Me2N
=
M2C12(NMe2)4(L-L).
W
contrast,
compounds
CO~
P
In
W2(0R)6(py)(C2H2>
[189].
Bidentate to
is
phosphines
L
(L
= PMe3,
PMe2Ph)
3M2C12(NMe214
+ 4L
-
2M2C13(NMe213L2
2M2C12(NMe2)4
+
--c
M2C24(NMe2)2L2
2L
cause
dissociations
+ M2(NMe2j6
+ M2(NMe216
of
96 (the
second
precipitate solvents
reaction
with
from
reaction
mixture,
disproportionate
further
they
the
PMe2Ph
only).
toluene
4M2C13(NMe2)3L2
The but
M2CL3(NMe2)3L2
compounds
on redissolving
* 3M2C14(NMe2)2L2
in hydrocarbon
+ M2(NMe2)6
+ 2L
600 Crystal CL = PMe2Ph)
structure were
determinattons
carried
out
and
the
on W2C13(NMe2)3L2 structures
are
and shown
W2CL4(NMe2)2L2 in
(86)
and
c1901.
NMe,
Cl I
L
wl Me
Y2\
*N’ I Cl
Bond
distances
CI
PMe2Ph
(87) L
are
W2C13(NMe2)3L2
W2C14(NMe2)2L2
2.338(l)
2.322(l)
WI-N
l-987(7)
l-940(7)
Wl-P
2_515(21
2.534(2)
Wl-Cl
2.457(2)
2.380{2),
W2-N
l-932(7)
l-931(7)
w2-P
2,522(2)
2.526(2)
w2-CL
2.411(2),
EW
=
2-428(2)
2.415(Z),
2.424(2)
2,430(2)x
(87)
97 Using from
the bulky
M2(NMe2)6
structure 2_32(1)g MoC14
in toluene
with
MO-MO
[191]_
The
with
NaSR
to the
2.7.2
have
chemical vary
spectra and
known
quadruple
bonds.
the MO-MO
the resonance
two compounds
of 42.7(2)O
the previously
associated
with
MO Cl (PMe > 24 34 of 8-Mo2C14(PMe3)4 former
are
thermally almost spectral
data,
experimental
There phosphines in all
been
with triplet
leads of
C1961.
spectra
depe
dimers
Linewidths
IR, Raman
containing
skeletal
and
and
MO-MO
stretching
the ground
state
modes
harmonic
dissociation
MO-MO
of O-0978
The
over
than
the 6 bond
energies
of
in l-propanol
the
B-isomer
(NH4)4[Mo2Br8]
conditions,
COS~=~
and
the 6 bond
and
spectral
temperature
above
has
is
compared properties
range system
the ground
and
the
with
the
state.
This
is
eclipsed rotamer. Together with -1 5200cm (15Kcalmol-l) as an
of
the barrier
interaction gives
give
dppe
compounds,
it is paramagnetic
coupled
only
about
the bridging with
B-isomer
chelated
[197].
in alcohols
The major
to rotation
of bidentate
the a-isomer
is obtained
with
torsion
the
of the Dppm
of
prepared.
these
distance
loss
magnetic
component
arphos
from
been with
C1951.
and
of about
in alcohols, and
data
bond
a wide
for
have
stereochemistry
Using
of 40°
a re-investigation
to the reaction
species the
400-500cm*1
to a value
dppe
according
easy
the highest
4148-
electronic,
the complete
angle
lower
In MeOH,
of
the
constants
between that
state
K4[Mo2C181
but
to
and 8-Re2C14(depe)2
examined
with
Interaction
of
Raman
increase
solvents_
ligande,
some
was
Mo(II)
have
3227
an antiferromagnetically
of magnitude
been
from
spectra
is diamagnetic.
bond
has
bonded
of compound
respectively.
a twist
measure
the quadruple
out
the bridging
length
have
this
with
products
of
tungsten~II)
of quadruply
class
force
estimated
which
populated
an order
have
has
consistent
and
M02X~(lI20)~
correlation
a bond
with
=
by reaction
(together the
M L 26
, w-s
c1941.
43.7(31°
is now
8-Mo2C14(dmpe)2
the usual
= 2.312(2)
prepared
of
prepared
[192].
ranging
8-Mo2C14(depe)2 and
and
It
this
Raman
constants,
proposed
revised.
IR and
estimated
isomorphous
number
carried
several
from
are
been
been
of the
The
angles
that
From
were
Separation
derivative
molybdenum,
has
anharmonic
bonds
also
been
[1933.
spectra
and
0x0
was
w=w
Mo2(SC6H2ZPr3)6
of a large
for
study
Raman
located
compound
have
revealed
and
of molybdemm(III
confirm
to 1440Hz
A detailed
the
M2(SR)6
diffraction
= 2.325(2)
prepared.
species
220
resonance
They
of
shifts
frequencies,
the compounds
X-ray
MO-S
molybdenum
similarly
bonded
observed
from
were
same
insolubility
g5 MO NMR
been
at 80°C_
= 2.228(l),
was
&uadrupZe
The
thiol,
in 1,2_dimethoxyethane.
MoO(SC6H2ZPr3)4) due
mesitylene
products
gave
three
were
a-
and
products
98
13-Mo2Br4(dppe)2 respectively, structural and
it
unit
containing The
analysis_
is
the
gave
brown
Bond
distances
the cage.
=
Hartree-Fock-Slater Cr,Mo,W)
to
together
with
the
three
were
the
using
CAS
internal
the
previous
spectrum SCF
is
in
the this
which
has of
could
crystallography,
2_218(1)A). at
The
Ligands 1984. length
to
in
be
X-ray
on
the
force
the
from the
at
Mo2
and
dppe
M2(02CH14
M-M
In
removed
being
the
crystallography.
(M
U,R
or
observed
=
constants
latter
molecules,
6 orbital8
photoelectric
higher
energies
bonded the
quite
contrast
to
earlier
It
is
showed
that
the
than
those
calculated
UV
been
than
the
PBu3
of to
to
in
the
and
suggested earlier
A in
the
molybdenum which
of
X-ray at W-W
oxidation
in
the
which
tungsten
W2(02CtBu)41
two
in and
in
as
which
the
isomers
Mo2(02CCF elegant complex
02CCF5
review the
showed the
C2011.
the
showed
studies
=
analogues,
monodentate
is
prepared
with
of
several of
Na/Hg
NaOAc.
for
in
one
be
and
adduct
this
series
analogues,
fail
NMR
by
one-electron
reported
that
thf
not
molybdenum
1:2
same
samples
a
6”
examined
paramagnetic
"F
e
structure
preparation
system
that
supports
suitable was
their
the
barrier
concluded
in
could
reversible
generation
31P
solution
liagnds tungsten
is
W2(02CCF3)4
crystals
confirmed
Mo,(O~CCF,>~(O~CCM~>_ phosphine
it
(WC14jn
bonded
give
give
tungsten
the
of
of
than
with
which
of acetate
form
undergo
(2.542(2)2).
that
and
The
c2001.
reduction
quadruply
determination
studies
calculated
techniques.
twist
metathesis
methods
in
has
W2(02CtBu)4(PPh3)2
W2(02CtBu)4
isomer
a
positive
oxidative
thought
been
the
usual
carboxylates
long
present.
by
equatorially
one
potential
corresponding
adduct
less
near
core
the
in
corresponding
only
labile
by
the
with
the
following
The
axial
structure
with
at
isolated
with
in
at all). This conclusion -1 19,OOOcm to a forbidden 6'
isolated
have
reacts
of
contaminated
to
why
crystal
presence
was
the
reacts
are as
A
all
unimolecular
of 4-
present
prepared
tungsten
Iodine
phosphines
6
has
is
peak
considerably
Mo~(O~CCF~)~
it
allowed
be
shown
explains
system.
it
but
potentials
probably
and
effective
NaC02CtBul_
complex
was
the
been
but
It
(if
of
method,
-160°C_
and
CM~(O~CH)~~+_
being
partial
[1981.
performed
W2(02CCF3>4
for
[Mo2C1814-
low
becomes
presence
Neither
EMo2Br8]
distances for
Mo2(02CH)4
and
in
very
W2(0CtBu)4
by
between
been
that R
rotation
by
a is
internal
2_520(A(av)
electron
0,
of
method
assignment
transition
have bond
shown with
rotation
barrier
the
=
ligands by
B-MogBr4(dppe)2
characterized
MO-P
dppe
confirmed
(1991.
optical
the
was
consistent
orbitals The
was
calculations of
It
a to
reaction
Z-569(1),
metal-metal
alternatives
is
ligand
Prolonged
calculations
analogous
considered.
spectrum
to
yield
bridging
involves
which
Mo-Br
two
was
of
mechanism
trans-MoBr2(dppe)2 are
and
@Mo2Brq(dppe)2
isomerization
that ligand
chelated
of
The
proposed
within
two
structure
for MO-P
the
solid could
state)
~HL~,",Ymp;;
are
much with
in
be
> 31;
consistent
bond
more the
solid
99 state
[2021.
structure Reaction
of
Mo2(02CPh)4
CMo2(02CPh)4X212evolution
of
N 2 forming
of
was
2.879(1)x
adducts
and
2.1142
(X The
determined.
Two
derivatives
have
been
of
groups
while
the
C~S-MO
(OAc) (MeCN) 2 2 of 2.576(5)8.
bonds
are
In
axial
axial
in
attempt
ligation, and
W2(02CH)4 a s,s
ones,
it
may
ligation
Pyrrole
rationalize
is
almost
PPh4Br
in
with
= 2.121(3)x
CH2Br2
long
and
The
their
identical
in
gave
with
axial
C2031.
isolated
almost
this be
the
dtc
to
MO-Cl axial
crystal
both
cases
the
It
is
cause
of
at
(pdtc)
reacts
more
usual
of
multiple
aromaticty
of
the
characterization S2PEt3
with
=
MO-MO
the
with
of and
ligands
with
of
the
acid
3rd
the
have in
is long
W-W
MO-O
distance
adduct to
in
despite
performed
transition of
bond
itself,
the
behaviour
and
the
on
the
involvement
the
W-W
metals
tungsten
in
The
PPh30
structure
same
a
with
the paper
to
shown
(with
form
character ring.
The
The
2.77(2)%
axially
been
than
1st
towards
row
axial
other
C-N
structure
S2PEt3
ligand
is
give in
also
Pyrrole
dtc
linkage)
ligands,
would
reported
to
coordinates
C-N
dtc
linkage
similar
(88).
single
[Mo2(OAc>3(S2PEt3)(PEt30)l(BF4)
2.1384(8)2.
an
W2(02CEt)4
row
form
l,l-dithiolate bond
HBF4.
and
contribution
Mo2(0Ac)4 has
dithio
pyrrole
in
that
different
complex
the
C2061.
which in
that
other
of
C2051_
calculations
for
two
2.64(2)
that
considerable
lower
acetate
The
example
system
transpires a
the
chromium
as
two
of
triflate
observation
MO
makes
with
formation
Mo~(OAC)~,
distances 2_135R(av)_
bonded
same
in which
cis-CMo2(0Ac)2(MeCN)612+,
MO-N
the
the
orbital
coordinate
than
reported
one,
are
relativistic
c&-Mo2(OAc>2(pdtc)2(PPh30) appears
long
a quadruply
orbital
compared
been
In
distances
W2(02CH)4(CH3)2.
Since
have
MeCN_
to
Xor-SW
u-bonding
bonding.
and
or
expected
been
is
(0 SCF > which has axial 43 32 This compound is the first
W2(02CEt)4(CH2Ph)2
of
have
distance
as
MO-O
= Cl,Br)
very
MO-N
triflate
an
by
with
equatorial
coordinated
the
is
and
Mo~(OAC)~
replaced
MeCN
rather
it
2.128(l)
MO-MO
pyridine
[204].
groups
of
=
in
dissolves in CH2C12 (N3J212hcrystal structure of _ The
determined;
MO-MO
(~~H)~CMO~(OAC)~X~I
structures
(PPh4>N3
[Mo2(02CPh)
CMo2(02CPh)4C123
(PPh4>2cMo2(02CPh)4C121 bonds
with
compounds.
because
lead the
to
preparation
from
the
that
described
reaction
in
the
dithio
PEt3
to
give
(89).
The
loss
of above
acid
form
f2071. Mo2(mhp)4
reacts
with
cfs-Mo2(mhp)2C12(PEt3)2 shows
strong
fluorescence
which
fluorescence lifetime
SiClMe
even of
33.8ns
3
has in
in the
the
structure
ordinary
[208].
presence
of shown
laboratory
in
illumination
compound and
has
a
100 Me
I
o’co ’ MO
/
5’L I
Bond
distances
c
O\PPtl
AS’
3
h14
(88)
are
MO-MO MO-O(OAc)
=
2.134(l)
=
2.115(7)
=
2.444(3)
=
2.370(7)x
MO-S Mo-O(ax)
Me
PEt3 Bond
distances
are
MO-MO
e
2.103(l)
MO-O
= 2.052(6)
MO-Cl
=
2.435(av)
MO-P
=
2_559g(av)
101
Mo2(R-1,2-pn)4 been of
recorded.
has After
bridged
A made
the
techniques.
Huckel
treatment
bonding The
is
the
A
based
on
been
8
CD
spectra
have
(bridged)
that
the
Boltzmann iodo
the
and
hexameric
isomers
only
the
familiar
been
triplet
influence
prepared
by
on
of The
lifetime
analyzed
in
levels
been
W6114
the
c2101.
energy
have
W6112,
extended
strong
smalL
1.4-3OOK.
has
been
from
a
be
has
resulting
lifetime
clusters
been
clusters
more
have to
range
this
include
has
the
orbital8
luminescence
populated
They WI 3
than of
appears
over
increases
[M6X814+
d-electrons
anomalies
with
ternary
The
cZuster
new
been
prepared
They
all
~~-0
groups
and
and
(two
to
connectivity
refluxing
an
isoelectronic
particular
terms
W6117
and which
interaction
of
[2111.
prepared
and
series been
of
of
Chevral
reviewed.
temperatures, potentials
interactions
their are
all
the
the
of
influence
the
the
All value
ions,
phases show
of
electrical
which
indicating
stability
of
the
that high
C2131.
species
LiZn2M0308
characterized the
Mo3013
three
0x0
one
other
formula
have
ionization
phase
compounds
contain
clusters
of
at
second
rhombohedral
Other
The
the
metal-sulphur
temperature
cluster
properties
= Ca,Sr,Ba,Yb,Eu,Sn,Pb)
structural
(90)
that
of
in
rather
d band
overlap
determined
determined. 4+ cW,I8) core.
(M-
correlate
in
and
concluded
bonding
the
and
orbital
tungsten
physical
M,II Mo6S8
2.7.4
was
and
C2121,
The
the
narrow d
several
of
the
(chelated)
it
physics that
constants
elements
and
metal
temperature
for
number
absorptLon
c2091.
dependence
the
emissions
lattice
too
3 has
as
a
the
metal-metal
emerges
though
temperature
(NEt4)2CMo6C114
the
of
It
even
decreases
exists
of
methods
Huckel
the
with
its
species
re-examination
using
and
Mo2Cl4(S,S-dppb)2
isomer
Hexameric
2.7.3
prepared
comparison and
Mo2C14(R-dppp)2
staggered
been
Zn3M0308
IR,
magnetic
cluster ligands
MO 0 0 3 4
by
(I),
containing on
cluster 6/2'3/3-
each
and (I)
(II) and
and
to
two
(II)
ScZnMo
0 38 diffraction
X-ray
within
molybdenum
one
and
each
unit
which other
have
bridge
clusters) one
unpaired
( III)
have
studies.
one
~~-0,
three
to
other
to
give
a
electron
per
[2141_ black a
crystalline
toluene
C2151.
solution
compound
Mo4(u3-S)4(p-S2CNEt2>(S2CNEt2)4
of
for
Mo2(S2CNEt2)6
2Ohrs.
Its
was structure
made is
by
shown
102
Mo2
S
-
‘C -
NR2
S
S (90)
C
R N" 2
Bond
distances
are
Mel-MO2 MO-US Mo-S(u-dtc)
Reaction
2.732
(5)
=
2.32(
1)-2.40(l)
=
2.51(l), 2.56(1)x
of
compound
could
and
has
oxidatively
the
compound
through
their
showed
it
molybdenum
Li2[Fe2S2(C0)6]
expected
and to
atoms
consist and
a of
two
with
=
-78OC
shown
in
(P-XC~H~S)~
structural
1)-2.54(l)
2.48(
at
structure
decarbonylated
(NEt4)4CMo2Fe6S-,2(S-P-C6H4X)6
bromide
(92)
be
which
MO-MO = 2.861 (6)Cav) MO-S
(NEt4)2[C12FeMoS4]
(NEt4)2[MoFe3S6(C0)61
give
other
=
(X
gave @1)_
= Cl,Br)
determination
two MoS4(Fe-SRI3 3 persulphide
on
cubanes groups
u2-q
The to
the
linked as
shown
in
C2161. MS-Xa
calculations 3_ The [MoFe S (SH) ] 34 6 The clusters. MoFe3S4 reported
previously
have geometry results
for
the
been
carried
selected of Fe4S4
the
out was
on
that
calculations
clusters
C2171.
the found were
hypothetical in
the
compared
cluster single wFth
cubane those
103
Average
bond
distances
are
MO-Fe
=
2.762
Mo=S
MO-uS
=
2.263
Fe-pS
=
2.156
= 2.262x
(92)
Bond
distances
It
has
are
been
multi-electron was
shown
Mol-s8
=
2.47(4)
Mel-S9
=
2.40(l)
Mol-S18
=
2.64(5)
S8-S9
=
l-99(5$?
found
that
(NBu4>3[Mo2Fe6S8(SPh)91
electrochemLcal that
it
is
the
reduction
reduced
form
of of
in
RN3
the
to
MeOH/thf
give
cluster
NH3,
which
catalyzes N2H4
reacts
the
and
RNH2.
with
RN
It
3
C2181. The bridging
double between
corresponding to
The
atoms
iron.
changed
one-electron phenoxide
MO
[MoFe3S4(SEt2>3]2(p-SEt)3
phenoxide
coordinated markedly
cubane
by
is
more
each
S 34 magnetic
The the
reductions
molybdenum
in [MoFe
cluster)
difficult environment
to
reacts
(OPh)
1
substitution. similar
(which
to
The those
reduce in
the
the
with with the
compound of
has PhOH the
double shows
parent
three to
SEt
yield
groups the
phenoxides cluster two
are
not
quasi-reversible
compound,
although
the
12191. MO/Fe/S
cluster
in
nitrogenase
has
been
104
examined
by
structure and
comparison
(collectively
a
variety
of
results
show
the
and
of
to
those
coordination
Two
EXAFS
cubane This
nitrogenase
in
result
one-electron for
the
of
and
MO/Fe/S
the
type
information
reversible cofactor
of
two
absorption natural
MoFe3S4
are
clusters
complements
edge
of
quite
is
near
MO/Fe
known
cofactors
to
the
consistent
edge
structures_
similar
containing
and
and
isolated
complexes
nitrogenases
each
The other
MoS
with
0 33 the
[220]_ reductions
molybdenum-iron
N-methylformamide
X-ray
XANES)
MO/S
XANES
the
MO-K-edge
called
synthetic MO
unit_
independent
MO/Fe/S
of
the
have protein
been of
observed
Asotobao*er
for
isolated
vine&n&i
[2211_
ACKNOWLEDGEMENTS
I
thank
reading
the
Penny
Panagiotidou
and
Katherine
McGregor
for
carefully
proof
manuscript.
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