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2 Zirconium and hafnium
Coordination CL7nistry Reviews, 80 (1987) 131-156 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands
131
I KI1xmY:‘r
131
2.1
I ON ..............................
Zirconium( IV) and hafnium( compleses
IV) compounds
.............
2.1.1.
Halide
2.1.2
C'ompleyes wi th O-donor
2.1.3
mmpkses
2.1.3
Complexes
N-donor
2.3.5
('ompleues with &donor
2.1.6
Hydride and hornhydride complexes
, ............
, ...
1i gands
133
..............
139
with
ligands
........
Iigands
....
2.3
Zircnnillm(T) rnmpunds
2.4
%ircvnirrm(O)
2.5
Cnmp\lnds
.......
, ....
compounds bonds
hafnium. The solid-state organometallic
OOlO-8545/87/$09.10
, ....
of
in
h .. , ...
.....
series,
t.he coordination
chemistry
compoilnds are
only
0 Elsevier Science Publishers B.V.
this
cbemjstry
of these elements in~l,~ded
150
, ...
152
, ........
.............
this
149 149
.........
, ....
previo1ls practice treatment
142
............
, ......
and hafnilxm(O)
wit.h metal-met;tl
. .....
REFI?RENCCE~ ......................
and
132
with S-donor ligands
%irronilrm(TTI) and h.qfnilrm(TJl)complznds
Following
, ...
..............
2.2
comprehen.sjve
132
when
153
, ...
153
, ...
154
review of
attempts
zirconium
and
is treated selectively, the
compunds
contain
132
The
reaction
acetic
acid
nn
molar
the
CsHfF5
is
[Il.
bepn
atom
stretching
f 1 uoroz
fying
doderxhedra
(M”
glasses
contains
dimer {r(Zr-F
also
that
an
network in
which terminal)
The
oxide
the
earlier
has
of
q
the
[CU,(H,O),,]~~, bonds.
2.048-2.107
flunride
A;
Ph%r6Fz&
radial
[Zr,F,4]6-
[Zr2F14]
r-(Zr-F consists
of
ion
fo~~nci /.rF,
!la%rFB
[a].
(15-.5X0 sit.es strA>-
Ii) [51.
[ 7 1 r>t
The
s t I’IKY~IU-C=
that,
are
linked
i s a pentros>mmet
~(xnmon
and
~
proTons
= 2.171, a
o-f
t,hnse
infqrrivalent.
ion
a
in
iOn analyses
ions
fi-
bridging)
t.o
llrn in
di t’fract
t,he
share
atom
Im
measurements
a neutron
and
metal guide
of’ a-w&e-share?
dist.rihllt
of
for-
the Raman spctra
zi rmni
two
for
a rpl iable
t*eat\lres
for
The
symmetric
da.ta as
st~xli ed
prpsPnt
Raman
z i rc>oni
chains
ncrupy
anti prisms
square
similar
7~rr-oni11m
ively.
are nf
son
the
of
locat,ion
The
*H,O
phases
Iwpn
r-espct
llt,i 1 i zed
cnrrPIatiorr
IS],
the
of
) have
structural he
ronment,
X-rap
anhydro~~s (‘sHfF,
cii t’fprent.
Ph
How~\~?r,
hit.
atoms
study
identified
%rFe
table
anglil.ar
hafnilun
S-ray
hydrogen
two
with
or
Sr,
c:ont.ains rnvi
per-t~~r&d
indicat,e
rshi
that
six
(‘ompari
cannot.
Ph)
c:onsist.ent
[CU(H~O)~]*+,
dense
or
M”%rF6
of
mod i t’icxtions
~~nknown st.ruct,ure.
Sr, of
differential
Cu, (%rF7) z lRH,O a
form
dqxnding
hydrate,
sp+xt.roscopy,
number
An eight-cnnrdinate
is
Fo1 lowing
of
synthesis the
environment
CM” = Ha,
avai
coordination
= Ha,
I ine
[ :I] f
Time
Us( Zr-F)
romp1 exes
crystal
NH,Hf2F,
and
t.hat,
;inhydmlIs
[Z],
SrZrF,,
v,(Zr-F)
in
CsZfHfF6],
pol~morphhism;
Rxna.n
and
to
yield
high-t,emprrat.llre
Ba%rF,
the
M”%rFs
the
and
indicates
irconat~3
vitreous
on
for
and
or
approar.r-h
diffraction
\l”%rF’,
fluoride
rsHfFS
c~oordinat.i.on
analysis
freqtiencies
florozirconates ident.i
powder and
iow-
as we1 1 as
This
compLex
vitreolls
thermal that
caesium
acp~e:nt~s preparations
X-ray
and
and either
rompnents.
properties
I ine
fluoride
compounds,
reveals
by
sllggcst.
PhZrF,,
PWrF,
the
K,HfF,
thermal
TV)
soLid
since
identified
DT4 data
for
of
of
ng
differ~nt,ial
for
two
ratio
crystal
in
hafnium(
convenient
The
by
yields
fbati
have
of
s
polyhrctral
2.185
threp-dimensional
by ric-5 +.p
k]. framework
133 of ZrF,C sq~~are sntiprisms, which enclose two kinds of cavities. cuboctahedral
city-itiescontain
cavities rontain
one
atom,
GihiLe the
pressures of Cs,MC1,
(M = 7.r or Hf)
(equation
have been measured, and thermodynami.c parameters for decomposition
Cs,MCl,(s or I)
solid
compounds
vapur
ha.ve been
pressures.
been reported. respectively), reaction
of
ZrCI,.2hH,,
M
derived
Na$fCl,
gaseous ZrClN,
from
the
X-ray powder ptterns
K,HfCl, and Cs$fCle
but
with
and NH,Cl at
temperature
of M',HfCl,
smmonia
yields
ZrsN.,, and NH&l ZrN,
1300-1400 'C.
(.A- =
thinsemioarbazone,
ZrC1,.2NH, ZrClN,
t.he
[9].
at
a
=
NH,CI,
IO.13
i
and
The
300 'C;
ZrN,,
at 800-960 'C; ZrN,
1.28-1.12),
ZrCl,~2NHs has a cubic unit. cell with
Zirconium(TV) chloride acetone
of
Na, K, or Cs) have
q
350-700 'C; ZrC1,,2NH,,
1000-1050 'I?; and
depndence
(a = 15.99, c = 13.21 k)
and NH,Cl at 750 "C; ZrClN, ZrN, at
(M'
(11
are cubic (a = 10.036(3) and 10.394(4) A,
is tetragonal
ZrCl,
of the
2CsCl(s or 1) + MCl,($)
and
MT,Cl
larger
112 t tiJ-coordinated lesd atoms [8].
Eq~lilibril~mdecomposition
(l)}
'extra' fluorine
The smaller,
Zr3N4,
ZrsN,, HCl
at
[lo].
forms solid I:1 adducts with aminop_yrine (1) and Infrared
Me,C=tWHCSNH,.
spectra
indicate
that
Me
M N
/
\N
I Me2N
'Ph %i
0
(1) both ligands are bidet-&ate. carbonyl.
oxygen
atom
and
t,hiosemicarbaxone coordinates
Aminopyrine coordinates the
to zirconium through the
djmethylamino-nitrogen
atom
[ll],
while
throllgh sillfur and the azomethine nitrogen atom
L121.
Vibrational
spectra
of
ZrCCI, *SH,O and
its deuteriated
analogue
have
and
2198 280490
2180
rm-I,
cm-l
{eqllation
[ 14
(3))
hands
l’( Zr07r)
].
reaction
The
yields
the
at of
oy-o-bridged
3[ ((Me,Si
[ ( I(MF~~S~.)~N]~Z~MF!]~O]
605 and [ ((Me,Si
584 rm-l
complex
[ ((Me,Si
wi t,h
ln
(2).
),N),ZrMe,]
t
, and v(%r-(‘I
)ZN}Z%rMe2]
the
)
hands
carbon
at.
monns-idr
, rwmpo~xxl
r-rystal
+ 2rx)
)ZN}2%r(0(~(Me)=(iFlez)
(Me)
]
(2) is
(2)
rnntrasymmetrir:
r(%r-N) hy
= 2.081
exposing
hours,
a
has
as
174.1(312
0.001
st.irred
a,
z-( Zr-0)
and
benzene
ox-o-bridged
%r-b-Zr soIut.ion
struCt,ure
=
1 .%O( 180”
q
of wit.h
1)
i\,
[lFt].
=
2.225(3)
[ { (cp)2ZrYej,0],
[ (cp)27,rMe2] I-(%-0)
i-t zr--(’ )
=
to 1 .Y3R(
the
,;,
nht;linFul for
air
I ) ,i and
sixteen
Zr-i)-%r
=
[16].
Solllbi HO(XMP,)
f
wi t.h
I i ty
syst.ems
A1.Zr(CCHMe2),,
measurements have
hIIt, failed
nonfi to
in
the
A1(~~Me2)3-Zr(rH~le~)4-T.
rmed
the
exi stance
provide
evidrn0=
for
nf
t.he
(I.
=
bimetallic
.~I)2%r(WIDI~2)Io
thf alkoside
LIT].
or
135 The vo I at.i I i t2; and thwma I decnmposi t,i on of
[M ( t.f’RCRlP)4 ] ) and
[M(CICRC)4I,
tkYn Rtlldic=vl hy VOlkO\ et RI. A variety or h7.a~; of
and
A similar
his(r\5-inden>-l
) have
t,he
has
and
[21,22],
and
= MP,
the
proposed
on
are
of
are
soIut.ions
the
correspnnding deri vat.i vest
)
[(175-Cg~i7)(~s-_(~4114N)Zr(a~ar)
j(S2CNRR’]
[(cp)zzr(dik)](S,CY)K]
= acac
A3 I of
IH and
bidentat.e
= a,-~
t.hese
(dik
complexes
coordination
abIt
ItI NMH spwt.ra, and
t,he
behave
or 1: 1
as
zi rct-mi urn has
which
show
dil,hincarbamat~
that
and
t.he
xant.hat.e
urwonrd i na t,ed .
1 ,3-l)i ketonate[(cp)Pl(dik)2(N0,)] have
[23].
aq\wous
t.n synt,hesize
) (~5-pyrrolpl
Wtrahedra1
hasi s
1 igands
1 ,3-di.1retnnat.e groups
the
have
Hf)
N, Wdi a I kyl di thi ocarbamate
sndiwn
used
salt.n,
Cllble,)
in nit mbenxPne.
elPrtrolyten been
or
at,e
hwn
and
alkplsanthate
Et,
by mixing
prelwred
(Q5-indenyl
[(~5-r91{7)2%r(aC;Ir)][SZCh~H’] hZRC ; R
chelates
(dik
[(n~)~~r(~ik)][S,rNRR']
been
appropri
proredure
)
ket,onats
lM(r~F,(-~F‘,(:F,~~Y)(Hc'tw~l-l,),] (M = Zr or
nt’ t.he typ
or aryl
[tcp)2%r(dik)]C’t
[ 19,201.
1,3-di
[18].
of’ complexes
R.,R’ = R I kyl
the
hen
a.nd and
prepared
ty
are
giyw
romp1 ews
[(cTp)M(riik)(NO,),]
(M = Zr nr Hf;
rcartion
acid
ha,f’ni IITI 1 ( 3-d i kc+.onat es rwrt.ions
ni tratewnt.aining
in
in
of
nitrir
dirhlornmet
fqi~~l ions
1 (cp)M(dt~=.m)~Jt HN$
(-1)
bane and
with
or
of dih
t,he
= acar
appropriate
or dhzm)
zirconium
1 ,‘&dirhloroethane.
(5).
Reactions
of
types
Typica
I
[(cp)M(dik)$l]
[ (~~~)M(dhxm)Z(N03)] t dhzmH
------+
or
(4)
20 *t:
[ (cp)M(dhxm)z(N03) with
nit,ric
arid
to
lrrl
[ (rp)Y(dhxm)2C1
I t IRXJ, the
formation
-
]
(dhzmll or
t,n
IWenzw)
1 ,3-rli ketonate and
t.wn nr three
(NO,),] prnd~vts
+ dbzmH (eq~~+tion
t (rp)Wl,(NO,)~4H,O
(5) (6)
(6)
‘r
Hvo, .-----+ -35 -r:
r~=~3~~~rtwl
of
[(“p)M(dhzm)2(~(~3)]
-35
(M = Zr or Ilf)
1(cp)Pl(dlzm)
----
[(r?p)Zr(ac~c)z(Nna)] t
cnmplcx~s
tri4.hylamine
t
I (cp)%r(acar)(NO,),l
(rp)Zr(‘12(N03).31120
i Ipnn
(quation
(‘i)
t.reR t men1 (8) I.
wi t.h
1 ,3-rli ket.one
'l'he[(cp)M(dik)2(N03)]
136
(cp)ZrC1z(NOs)~4H,0
t 2dikH t PEtaN
(8)
[(cp)Zr(dik)z(NO,)l
-----+
+ 2[Et,NH]Cl+ 3H,O
and
TR
tetrahydrofuran. bidentate
indicate
speotra
and suggest that the nitrate
non-electrolytes
essentially
are
complexes
](cp)M(dik)(NO,)zl
that
the
in
ligands
l,%diketonate
Iigands are probably hidentate
are
as well
124,253. Heterocyclic (dik
is
the
tetrakis(1,3-diketonates)
anion
of
the
tyyx, Zr(dik)n(~HMez)s_n
4-acyl-3-methyl-I-phenyl-2-pyrazol-5-one
of
(3)
and
R Me
-3
OF
N/ \ ,t
'N
I
Ph
(3; R = Me, Et, ph, 3-ClC,H,)
II q
1, 2, 3, or 4} have been prepared by reaction of stoicheiometric
of
the
pyrazolone
complexes
are
composition complexes analogues,
and
Zr(CYCHMe2),~HOCHMe2
monomeric
in
boiling
Zr(dik)(CCHMez)a, exchange and
alkoxide
they
ligands with
or
NH4)
are
&Hf(SO,),(H,O),, sulfates
have
complex eight
anions oxygen
investigated
in which atoms
from
2.283 A), two monodentate
Me&OH
two
of
[271.
[28], and
hafnium
atom
bidentate
sulfate
amounts These
reflux. the
compounds
of
The Zr(dik),(CCHMe2)4_n
yielding
Zr(dik),(OCMea)+_,
giving
the
insertion
(n = 1, 2, or 3) [26].
the
ligands
systems type
(M = Na, K, Rb,
M,Hf(SC4)atH,0),,
IR spectra of the sodium hafnium the
has been determined the
at
for
isocyanate
sulfates
complex
[NH,]4[Hf(S0,),(H,0)z]~ZH~0
except
formed in the HfOz-M,SO,-Hz0
and MsHf(SO,),(H,C),
been
with
phenyl
products, Zr(dik),jNPhC:(0)OCHMez),_,
cs,
benzene,
benzene
which tend to dimerize.
react
Among the compounds
in
X-ray [29].
crystal
This compound
is dodecahedrally
sulfate
structure
(r(Hf-0)
q
contains
coordinated
1igand.s tr(Hf-0)
of
=
by
2.223,
2.067 A, and two water
137 molecules
(r(Hf-0) = 2.196 A).
edges, and the monodentate
The bidentate
sulfate
ligands
ligands span the dcdecahedral
and water molecules
a
occupy the B
sites. Standard ra~orimetric
enthalpies
measurements
Hf(SO,),-4H,O
of
formation
for
at
Hf(SO,),
298.15 K
(A%
fluorosulfates,
Zr(SO,F),,
and Zr(OzCEle)3(SOsF) have been synthesized Zr(OZCCF3),,
spectra,
compounds
anhydrous
the fluorosulfate and
COtlIpOUll&
good
by
complex
the
ZrCK&,
(Csv
Lewis
or
mol-l)
by reaction of fluorosulfuric Zr(O,CMe),.
sytmnetry) in
acids
and
reaction
has a
On
form
sulfonato-complex of
[(~p)~ZrCl,]
five-coordinate
bent
basis
by and
coordination
with
IR
All
complexes
four with
[31].
AgCFsSO,
metallocene
acid
of
in the first three
[(cp)2Zr(CF,S0,),(thf)]
Cl3 C23
(4)
the
Zr(O&Pie)a(SOaF).
oxide, pyridine, and 2,2'-bipyridine
The trifluoromethane prepared
determined
ZTYO(SO,F)~, Zr(0,CMe),(S0,F)2
ligands appear to be bidentate
tridentate
are
triphenylphosphine
This
been
have
-2230.1 f 3.4 kJ
(AH+ = -3492.8 + 3.3 kJ mol-l) [30].
Zirconium(IV)
with
=
has been
in tetrahydrofuran.
structure
(4) in which
there
Xi-(011 SC,1ut
139 (b)
complexes of the typF? IZrOX,L,] (X = Cl, Br,
aromatic amine &oxide
N(:S,
or
~Zrol,,]
and
NOs)
2,6_rlimpthylpyritline mono-+oxidej)
(c)
[C10,j2
&oxide,
(I,
=
or
HphenNO
of
the
pyridine
N-oxide,
lI,lO-~henanthroline
[Z17];
dimethylmrthanamirie M(So,),(dmf),,
compleses
MOS04(dmfl(HzO),
WI=
i%Clz(dmf)z(HzO)z,
and MO(CIII)(NO,)(dmf) (M = Zr or Hf)
[38].
The been
t,etrakis(l-oxo-2-pyridonat.o)- compLes,
reported
in connection
nine-coordinate
2. I .3
c’omp
thori.llmcompound,
I m-es
Sevrral
wi th
papers
the structure and
and
five-coordinate
S -&nor
bent
an
X-ray
structural
study
of
the
has
related
[Th(CsH,NO,),(H,I))].2H,O 1391.
1 igands
have appeared
molerular
monothiocarbamate
(r(Zr-centroid
with
LZr(C,H,NO,),]-CH(71,,
during
the past
rearrangements
complexes. metallocene
cp) = 2.216, 2.222 A;
An
of
zirconium(W)
X-ray
structure
year which
(5)
study for
has
shed
light on
dithiocarbamate estahl.ished
a
[(cp),ZrCl(S,CNQ.)l
(centroid cp)-?r-centroid
cp) = 129.4').
(5) The zirconium
atom, chlorine
atom, and the two sulfur atoms of the hidentate
140
1igand
di thiocarbamate ~rpendicular t/he
to
two
cmwling cnord
in
txmd
length
.i};
0.3
kJ
mechanism
of
dithiocarbamate equi
Ii brium
probed
by
similar
rxtended
for
1ong
(r(Zr-C*l thP
of “(1
f
the
im-r>lvp
pri nr
possibility
mnlw~~lar
monothi
met,al locene
t, i on
of
orbital
Zr-S2
structure
(6)
terminal
,
A($(
28 thr
t,he
a.n;llogo,~s (‘)
2.5
= 67.7
K-l.
l’htin
the> Zr-8,
bond.
ruptllrP
have
bond
bond
aft’nrtlpil
C’L-FU’ bond
of
.\; atrd
%r-S,
thy
.J mnl-l
thP ThP bcn
[ilO],
1 (cp)zZri‘l
with
%r-(‘I
The
s-1;
Calculations
ocarhamato-comples
lateral
NFN nt.\lriy has
f
of
2.5.56(Z)
=
in
al-Kwt ruptllre
thp
grolaps
8.6 = -4
Iy
mPal1RP 0 f
to
)
longest.
near
thf> crnt.roids
bonds
MHz ‘II
A.@ rota
and
11’) cornpI++;,
methyl
is
that
I iganris +
the
A Xl0
eyrhange /i( 25
may
atom
grolip,
zi rcwniwn( 4).
involvw
and
HG-kel
xircnnillm
are
a
pfane
I npw tadi eng I
67+8kJmol-1;
and
analogous bent,
for
process
geomptry
The
dist,ancen
=
1igand
mi rror
Iy
these
rompleri:
t.his
the
1musi1al
dat.a
AF8
by
n5 +yr
= 2.6:15(2)
kinetic
mol-I;
quasi
nhservrd
(r(Zr-S1)
L(cp)2Zr(‘l(S,CNMe,)] f
a
cwordinat.ion
yet
normal
following
defined
at, Lwhed
sites
I engths
is
in
%rCIS,C’,,
= 2.723(2)
r(iY-S2)
the
plans
~a.1 I y
the
i na t i on
Zr-S
the
symmet,ri
lie
(SWNMP~)
has
I
monothifxarhamate
a
1 igand
(61 oriented
so
as
congested,
lateral
congested,
interior
r( Zr-0) 2.236 76.1
= 2; .;
I(cp),ZrC1zI
to
(centroid
with
the
coordination
2.249(4)
Cl-B-43
place
adjarw~t.
i;
I-( 7r-S )
138.1 anhydrous
‘1.
oxygen
site
site
cp-l.r-cwt.roid =
smiler and
t-o the q
the
larger
chlorine
2.641(Z) cp)
atom
=
128.5
.;
NafSOCNMe,)
in
hoi ling
S-Zr-0 was
atom
{r(Zr-_(.:I
r( Zr-rent
[(cg)*~r(:L(SO(,‘NMe,)]
sterirally
sulfur
atom
,i;
t.he
in
roi d =
)
in
preparw1
the
= 2.5.X)( cp)
62.0
dichlorometh8nP
more 1~s~ 2)
2.2:30,
=
~; Cl-ir-S by
react, l-11
.I;
1.
i on
r of
141 Hafnium(
IV)
[ (cp) w ( s,wm
dit,hiorarbamat,es
J ) 3 1 I rm 1 = Et, by
been sgnthpni 74 molar
Al 1
ratio.
solution,
and
of
of
these
rF? sppctra
five-cnordi nFtte
met8
[
t-xvt
[ ( cp )M( s,(‘:me, ) 3 ]
(M
t.he
lloc~~e
(cp)Hf(S2CYRR’)3]
[
Ti
j
dithiocarbamate
like
are
Zr)
in 1: 1 CT 1:3
non-electrolytes
[(cp)ZHfCl(S,CNR3?')
structrlres
or
Na (9,CNRR
in
ligands
have
[(cp)2Zr(ll(S,CNEt,,)]
pen tagona
143,441.
hi
i
are
complexes
[40],
pyramidal
Analogous
Like
bis(fLuorenyl)-
-~alkg‘l~~arrt.~rato-cnmpt~ses, [(17s-(:13~9)z~~1(~2~)~)i (n = Me, ha\-e
and
(cp),HfCl(SZCNE?R')I
monomeric
the
compnlrds
=
and
are
s11ggest. that
PrPs\~mabl y,
t.he
[ (cp) ,IIfCl 2]
complexes
hirirntat.e [42].
and
types
I(-r,H+Me; H, ~yrIo-(:~H,; or II, cycle-C,H13) have
waction
of
t.he
Et,
0r
CHMe,)
been preparecj by reaction of equimolar amounts of [(Q~-C,,H~),Z~C~,J and in
K[S,MR]
dimethosyethane
I,ow-temperature i
equally
ntenne
septets,
[15].
lflNMR
isopropyl
attributable
to
spectra
methyl a
of
doublets
ligand
[%r(S2CN(CHMe,),],] and
two
conformation
equally
(7)
in
exhibit
intense
which
the
two
methine met.hine
Zf
4
(7)
protons of the inequivalent Ligand.
4t
higher
coalesce
to
a
isopropyl groups are located in the plane of the
temperatures,
single
doublet
the
methyl
doubLets
a
single
septet,
and
hindered. rotation about the C-N single bonds.
= -39 f 5 J mol'l deg-I.
of ZrCl, with
Na(S,CN(CHMe,),)
Low-temperature [Zr(S@XMe2)4] consistent (8).
methine
respectively,
[Zr{S2CN(CHMez)2),J was prepred
Variable
temperature
to
by the reaction
in the presence of triethyl phosphite [461. spectra
'H NMR
the smtrum
due
= 45 & 1 kJ mol‘l and
of
the
monothiocarbsmato-complex
can be interpreted in terms of four overlapping
with
septets
Rate constants for this process
range from 20 s-l at -25.0 'C to 670 s-l at 21.0 'CT;A# A$
and
expected lH
NMR
for the Czv dodecahedra spectra
indicate
the
methyl peaks, stereoisomer
presence
of
two
142
(8) dist,innt
kinetic
processes:
rearrangement., (b)
Coa I.escence deg-l)
Ati=
f
AG”(78.2
process
douhl e
bond
1; ‘C)
for AS*
the -34
q
82.7
q
L’I’P f
i
and analogous
[M(S2CNR2)_,J
rearrangement,
mecyhani sm for
thiourra
in
,Cbond~d
thiourea
dimeric The
moleclllr
is
rconium(
= pyridine,
bot.h
Cal 0rimetri.c
at,t.ached
‘Z,tSdimethylpyridine,
or
Zr)
t,o
to
t.hr
of
in+ract
IV)
with
comp
Z-methglpyridine, q~jnoline,
the
I ex~?s
C--h:
1 :2
complex
with
and
[‘vi
0.2;
= 7P.2;
The
15.
or
f
greatzer
(S(X’YMe, ) 4 J a
p~lytcpal
with
metal
t.hiollrra
c,hloride
and
1 :1 addrrr~ts c>ontain
ng
has
oh lorine
bepn that
al.oms;
srlggestrd on
I y one
a
l.181. t h i ourpa
adrhct.s ; t hf> st~c~onc-l I h iolllTc’:x
VIR
hydrogen
Whet.erocyc
or
‘/;,
HfCl,
the
hri&i
2-aminopyridine, W(bipy),
H’I’P are:
wi th
of’ t.he
i ndi
the
47.1
[ 47 J .
t,hat and
mol-’
=
suggests
ZrCl,
indirate
in
f
son
complexes
amnunt,s
measllrements metal
qi
q
process
terminal
C)
the
rompari
I((~~2Eu’)21‘SJC1311~12M(:13(S(:(~M2)2}] and
appe_ars
Oxozi
Ti
for
A,+
in
stoir>heiometric
and
the
(kJ
A(;5(-53.5
values
9Yk5;
IR spectra
1igands
-53.5;
1 and 2: 1 adduc:ts
mixing
acetate.
st,ruct,ure
IF? spectra
molecule
(L
ethyl
=
t he met a 1-centered
1: by
=
=
about
parameters
activation
‘&
(%r(SOC’NMe2)4] (M
rotat.ion
1 igand.
and
Al?=
of
Moisture-sensit.ive prepared
the
Corresmnding
0.5;
rigidity
been
mcta I -mw t,~r~d
invn1vin.g
involving
(HP)
are:
I‘i .
stereochemical
have
in
(“C)
t,empwatwes
J mol-1
(I,‘I’P)
and
a high-temperat,ure partdial
40
process
low-temperature
a
(a)
H(phen);
Lic
ho&s
[‘18,49].
Iigands,
%rrX,[,
2,4-dimrt.h~~p;vritline, II = 4 r;hpn
\
J (‘1,
b,
143 L
I
ot
n
r’lc!,;
or
t hew
prch
2 when X = NO,,
q
arc?
complnds
Iorate
or
non-e
dw-iVat imps,
NW),
1 ect
which
rol
have i n
yt.es
h&we
heen prepared
as
1 :2
ni
in methanol .
t.rohenzf=ne
except
eIectm1y-t.e~.
Al I the
for
Infrared
spctra
indiPatr5:
t ht=
(a)
:ShPterocqr
I ir
hPt Pro-ni t rc-xgen Sami nqyridine
atom,
and
the perrh 1orat P w)rnp,Iuxk
f (‘)
thts n i t rat e I igands
(11)
I tar NCS- 1 igands
+~oxi rcon
1 i g;rbrls
i II
l\:)
i rrm(
are
rest-ts
or
(‘IO,-
in
a variety
tri le,
bipy,
s t IKJi +--d ( Xi ] ,
anfi
z i rconi I em-hydrogen
I)iazna i ka.ws
((cp)2%r(l~)~‘l rorikain
I,,
$-N,
H’.$=N=N
respect
1ai.f~rit
C.1, Hr,
or
2
_I )‘I-“,
of 1;
n
2.12(Z)
( i-l XI--M+ ) r’(7.r~Cl i
A
= q
i
ot‘ thr
irit-li(‘atP
1- )
l’he
=
hnnd
.i
in
(lo),
in
(12))
is
1,
also
d~lo~alizat~ion
t.hene
int.a
or
other
(lo), lateral
=
2.37(l)
and
metal locsncn and
or
that (10)).
that
t,he
Zr-N
2.21(l)
A in
hond (ll),
coordinat~ian i
lengthened
‘I’he X-ray
6),
has
CH,Ph)
(9)
interi
or
zirconium-carbon
Me
=
4,
compundn
indicat.e
ji in
I igand.
3,
and (12)
2.103(9)
si,grrif’icantly
2,
t.he correswnding
(wpr8tions t:he
t.hp
of
bent
(11))
r(%.r-(lli$h)
hydrazonatc>,( 1-j
ll-f+l~~tt-ot~j~
(H
t ban
t,o
that.
zirconium(lV),
q
insert
ligands
(10) ,
I ongcxr r(Zr--NR)
(12)].
2.549(51
II~-attac~ynent stlidiw
in
2.357(6)
WzKt)
five-rnordinab
nt’ comprrnds
i;
t ion
[ ( c~)~~.I-I?~]
pielding
is
.25-2.28:1
decompni
= Ph or of
hydraznnatn(
urw bond
I
1, ( r-(%r-WI? and
ivcly,
!V’-bonr~ed
\-VI\- cy)-st R I ntnrt
(H
bonds
These
indicate
[ .52] .
7,~‘ I 4 rci t h ‘i( GII,NHNH, or
bm
pyridine,
OT- phen).
(X
-l’he t herma I
b&donor
%rO(NCSe),L
and IR. spert,ra
~~~~‘,~I,NI~~.ll,],~-/r~:I,_,~2~~YH~~FI,’,),] hyClra7j np hy-lrc>r~hI orid+.
and
ZrC,( txSe) zL2
and
romp1 P\;PS q
0-
tw
RTP r~htalned
thrt rwwt.i on of
at.om [SO,51 1,
(Hu,Sn ) ,O,
N, :V-dioxide,
rthaneni
S\lklst i tilted-ph+>nyl hydrai-idr,( 1-) from
t.he
of
i ens;
of
the
of
pheny-1 hydrazine)
2,2-bipyridine ytes
atom
the nitrogen
Ph,W,
ww t Ri n &T-bonded t h i or’yanat P 1 i gands
t.by
with
,WOXidP,
hydraz i ne,
non-p I wt.rol
through
compl wcs
p?ri d i np
(1, = -I-aminnentipyrine,
amino-nitrogen
hidnni.at,e;
arc4 roordinated
yielding
%,.l-clim~t.h?-lp?lrirtincl,
romp1 wes
a,~
the
through
to the met.aI ;
rwntnj n 11ncoc~rdinated
srl enwyanate
mf~t.hiuwI
(I. = nntipyrine,
t.he
is not, at twhrd
(fl)
cnnrd i nat e
are
1 i gads
in
because
results
nV~‘r’the C-N-N unit
sib and
(ll),
and 1531.
of the
the IR
144
( rp ) > % I----
[(cp),ZrR2] f Kf2(‘=N=N ___)
(9; R
q
‘u-it
(9 1
Bz, R' = Ph)
(10; R = Me, R' = Ph) (11; R = Bz, R'
CCKEt)
q
(10)
(cp),%r(H)Cl), + Ph>f:=N=N --+
chlorine-bridges
WI the basis of the JR spect.ra [5Fi]
[M((NSiMr,),SiMP,}2]
Thermal dwomposition 60
‘c
and
lV2
t M(:l, ------+ 'LMc.1, 1 (NSiMP3)*Si?k2)
yields
a
[ (~r(lHSiMe,~SiMe:,[N(SiMe3)2])~J, having fused, planar,
rings
and
ana 1ogous the
the hafni
q
2.04-2.09
d~romposit.ion
prcdwt
A);
ring
cent.ral Zr,C, INII camp I PYPF
bridging a
cart~nr~
st.nlcturP
(13)
in
rings adopt a "tub" conformation
four-membrred
and 2.19 k; r(%r-N)
= Mr, Ft , or ('lI,SiFle,) at (J'?
of [H,%r(N(SiYe,),),]
mm Hg
,
the dihdral are
111
[~Hf{N(SiM~3)2J2] WFi.9
inolat,ecl
t(kf(:HSiMp,kSiYe,[N(SiMea)zj(r'y))z] [St;].
(11)
anglw
_ and 123
whirh
three
(r(7r-I:) = '2.15
h+t.w~Pn t.he tin %rNSiC
.
(R = Me, as
~v~mprod,
the
[n
the
I+,
CRSF
of
t-he
or ('H,SiPlea),
pridine
adduct,
145
H NR; 1 \ NR’ ‘C --Z/I I SiMe, R’N I I ‘h--C
Me,Si
I
\
R;N
H
(13; R' = SiMe,) 1,2-his(dimethy~17h"s~hi no
of
RPact i on
[(MC~1,SiMe2NSiYe,[?j(S~Me3)*]]~]
(M
=
%r
or
) et hane
at. room
Hf)
temperature
~K,?1(Y(SiM~,)2J2] (M = 7r or Ilf; N = Me, Et., or W2SiMe3) the his(metaIlaryrle) an octahdral 'L. 3 1 6
=
monn,sidP
rarbon
or with
at 60 'C affords
xirconilnn comples
has
tris(chplnte) strurtllrp of' jdea1i~Ffd c-Z s:mp-t.ry (14) {r(Zr-C) =
T(Y.r-N)
,A ;
TOP
[M?~~SiMe3)z(dmp)].
with
(ctmpe,
2.0xX
i’\;
i-(3-P)
=
20 'c)
(20 atm,
in
2.X52 pntane
kmpund
k).
yielding
(14) rea&.s with compnund
(15);
the
proposed ntrncture of' (15) is based on it1IWR and 13("NMR spectra 1571.
ii”’
CH2 Me2
P 'd, P;;r<
*A
\
,SiMe2 I
I
Me2
PI,
,NSiMe3
p;
NSiMe3 Me2
:
1 ;r< _
NSiMe3 \ ,SiMe2
Me2 0,
1’
CH2 N
SiMe2 / ,NSiMe3
C
SiMe2
!H,
(15)
(14)
RPartinn {H =
Me
r:omplPWS
or as
II-1 NOW and
of
Vh)
the
with
phosphorus F#'l, (M z
~olnurl~ss,
3lP{lt1)
air-
containing %r
and
NVIK spctra
or
Hf)
moisturcof
these
disilylmjde
LiN(Si.Me2(7H,PR, )2
yi.elds l~l,(N(SiM~,~H*~*)*]~] sensit,ive orystalI.inp solids. compundn
are
consistent
with
146 stn1ctruY2
has
which
(16),
been
-stab1
ishpd
Y-rav
hy
t’or
14i t’f’rart
i on
arp
hldentatr,
Cl
(16;
[ZrC:lZ(N(SiM~*(:H2~e,),},]. wi t,h t,he of
t,hP
two
The
\uv:oordinatcu;l
equatorial
approsimatcr(Zr--Cl)
q
The
symmet,ry
2.460
:\;
N(SiM+(‘H,PRR,),
bulky
SiMp,(‘H,PR,
plane.
C2
R’ = SiMe,cH,PR,)
and
Cl-k’1
grarips
resulting
is
HfC14,
yielding
and
can
be
the
[Hf(BH4)4]
by
to
amide t.he
reaction
[Hf(BfI,),{N(SjM~Ft,(‘H,M”le,),)] dinuclear
trihydride
rcith
[ZrCL2(0Ye3)(RHPz3)]
[ZrCl,(CC’Me,)
(HR( 3,5-Me,&,),]
correspond& of on
the
more
stet-inally
rigjd
at
5
ng
or
i.n
scale
hindered
twist
t.hp
of
hasps
up
heen
(A$
z
(Wt.a
1~10 .C.
The
the
synthesis
for
{lIR(3,.i-Me2Pz),)l preferred
prepred
[60,61].
)]
nf the
e
C~0l~)
the
PZ)
and
of’
the
T<;it,h
one
JZ = 1%~)~ vhi 1~ the is
stahl
of
r-nmpl ~YCXT are
st.creochernic~al
ly
mcvhani sm i s
J sPrvl?s or
IV)
r~lar:i-ion
rearrangement
(R
been
gives
nr
) ( WPz,
2 1r.J mol-1
Ul,Ph,
IYi’ f
romplexes
[ %rCl 2 ( WMr,
[%rc‘1,_n(OC~l~,)n(lSR(3,.5-MezPz)3)
also
Me,
Wlea)
hy
[Zr(CX7M~~)R2(HR(3,5-MFf*P~)3)]
have
=
PVYSS
Treat,rnPnt
Ru,
tri-tert-hut.oside
deri\-ativps
of
zirc:nium(
CHM+ ,
of
has
2.1196,
1591. of
1ZrCI,(~~3)(Kn(0,5-Me,Pz)3)
for
prespnce
nr
prepared
56 f
[%rC12(oCMe3) tx
[60].
material
H,
The
=
15Hl.
I,i [f&j.
[~%rc:13{1~3(3,fj-M~zC’z)3)]
t,oluene.
NMR time
t.emPeraturPs
trigonal
stat-t.i
Ko(?le,
=
st r-la-trlr‘p
[~lf(l~H,),~N(Si~p,(‘H,~le,),)
complcvzes
have
1
[I.rCl,(RBPz,)]
equivalent fluxional
(R
t,~ sides
LI~fc~I,(N(Si~lP~l‘H*t’Ple~~,~,I~fCl~
excess
tert-hutoxide
opyx~i
F(Zr-C) ‘1
[ {Hf[N(SiMcsz(‘H2PMF?,),]],(H)3(BH,J,]
Poly(p~~vrazcrlyl)borate t,ype
in
complex
I,ewis
%.iW,
= 119.1(l)
innntps
comptps
an
on
octahc=draI =
N&-N
monomeric with
lc~abct-l
distort.&
= 135.42(A),
“mono”
converted
heing
(T(7r--P)
chiTa
[ Ht’C‘l z (K( Si Fle2(‘t12Wk2 ) 2 } 2 J di spmpnrt
which
ligancts
as
a Useful
derivat
alkyl [Sl].
]
iv+=s
Di (n
=
2
or
and 3)
147 The or
sryl
H-qui no1 i nolat.o-romp1
) and
pr~pard
h;r,
appropri
ate
[(cp)~7,Zr(8-O-quin) mixing
are
S,CWW
121%J .
analngol~c or
S,(loK)
to
[ (cp)2Zr( 8-O-yin)
] [S2COR]
aquenlls
sodi urn
o+Il kyl uanl hate and
.=xes
solutions
(77;
HI,)
in
compolInds
t.hp
ment innpd
the
=
of
Me,
in
Sect
inn
1 : 1 PI ect.ro1ytt.e~
HL;
R = H,
alkyd
have
heen
and or in
the
ptfissi.um ni trobnzene, (V
q
2.1.2.
triethylamine
H
CHMe2)
q
[(cp)7Zr(dikJ]Y
reacts
of
or
[19,62] arp
1 ,?I-dik~t,onato-drrivativ~s
presence
(17;
Et,,
(RR’
1
[ (cp)2Zr(8-0-quin)]ll
hr,.~dialkyldithioc~sr~tt Thwe
I)ichIc,rnt,iR(irIIJ~rIYl)ZirCnni1lm(TV) hasps
(R
] [S,CNRR'
rd th yielding
C6H4R
2-Me,
3-Me,
4-Me)
salicg~~ldimine complexes
Schiff of
the
type
148
H -N t
‘N
/*
H’-3
R
Ph
R = Ph,
r--,
C,H,O)
(18;
M,;
(20;
H,L' ; R = H, Me)
(19;
HI.,;
R = Ph,
r----l
C.&O)
(21; H,L')
OH X H
(22;
H,L'; X = H, S-Cl, Fi-Br,5-NO,,
3-O&,
5-O%,
3,5-Cl,,
5,6-benzo)
149
and
I
151
R2
(33)
The reaction so
red-brown of
111 NhR syxtrtra
quivalent,
phosphi
(:sHs
to
prnt nns
with
[ (c~)~WI~]
I ut i nn .
the
[{(~p)~M(F?le~)}~]
prot.ons
two
do-hr
31P
t.wo
and
a
nllclei
st.nxtltre
i dgcul
equivalents
t.hess
of
%r or
(M =
of
complexes triplet.
.
‘I’he
(24),
with
Hf)
compl~~cs,
I.iFTle2,
exhihi
are
t. a
t311e to
virt.ual
spect.ra
are
ohtained diamagnetic
sharp
singlet,
cn11p1 ing consi
significant,
‘Z,r.
by
due
of
t.he
stent
* .%I-
in to
PMe,
wit,h
a
interact,ion.
Me2 CPI,,
ip\
,,\ CP
cP iMiW
/“‘\cp P
(24) IZearti
nns
of
resell
t, in
give
[(I-~)$LY~]
the
[
cl savage
Photo
(S
[ ( (?leq)z%rH(ti-H)
)21
ic
I ene
t.n
paramagnrtir of of
~(II~-c,D~),~~L,I,
in of
another
give ]
[73]
zi rconilrm( [(c’p)2%rcl*l
i.4
G,
r;hirh
i ndicat.Ps
halogen-containing
and
ouidati
on
of
species t.he
metal
t.a
75 of
.C and
It,
sol ntions
a
benzene
formation
i ndi.cate
r:oritplPX ~irccvri
of
of
the
rlrn( T1 I )-hydride
dark
of
purple
presence
which
,
slurry
of
a
with
rearts
perhaps
species,
. Tl t)-hydride are
is
at
evolution these
7:ir,conium(TIt)-h~r~ri~jC3
(PhCrCPh)
i t.t,ing
heat,ing
r~s~~lt.s
[ (WI-p)z%r(tl)
spl
bonds
i71].
prnlong~
13i ph~~nylac-et,;v
solrlt,itrns
metal-phosphorus
EPR spectra
sn l.l~t.ions. pai-amagnet
the
= halogen) or
Lysis
wi t,h
{ (cp),M( Wle, ) )2 1 oompl wes of
reduced
not, observed t,hat.
t,he
complexes wi t.h when
are
also
produced
magnesium. t,he
experiment
zi rnoni um( T‘II ) -h:-dri
rl~
when
A
‘H
i.s
repe2t&
is
thf
hyperfine
prociured
with by
152 abstraction
hydrogen
from
zirconium(JTI)-hydride reduced by magnesium
a
complexes
cyclopentadienyl
were
observed
by RPR when
photo&is
studies
Led to RPR characterization
the
a
sol.utions
zircnnium(TTT)
in
cyrlohesane
species, The
hydride.
[ (cp)zZr(PEt,)R]
contain
[(cp)zZrRz] complexes are phntolyed
2.3
was
of
(R = H, Me, cp, or Cl) have
of a number of zirconium(TTT)
and
[(CP)$rc11, that
[(cp),ZrCl,]
in toluane or methyl
[(cp),ZrR,l (R = alkyl or aryf) or {(cp)*Zr(R)Cl]
suggest
Additional
in the presence of alkenes or alkynes [76].
Low-temperature
[(cp),ZrRl,
ring.
including
EPR
adducts
spectra
r&en
the
the presence of PEt, [77].
ZTRCONIuM(f) CWlFWNDS
The layer structure of ZrCl and ZrBr can be intercalated with oxygen and hydrogen atoms yielding interstitial derivatives of the monohalides. Cl or Br) reacts with ZrO, at ca. 980 “C according to equation
ZrX + r1Zr0~ _
and ycan
ZrXOy + riZrOx
take on values up to CA. 0.4.
consisting
of
four-layer
slabs
ZrX (X =
(121, where s
(12)
The pure monohalides have a structure
with
stacking
sequence
X-Zr-Zr-X.
X-ray
studies have shown that in ZrXOUv the oxygen atoms are randomly distributed
in
tetrahedral interstices between the double zirconium layers of an expanded ZrX structure. ZrC,
Reactions analogous to equation
ZrN,
ZrF,,
or
Zr,+,S,
and
attempts
small molecules were unsuccessful Guinier ZrBrHoe5,
X-ray
ZrBrH,
data
ZKlH
also
indicate have
zirconium
tetrahedral
layers;
interstices
photoelectron
the
intercalate
hydrogen
between
the
that
expanded
formation is accompanied by a progressive adjacent
to
with
several
the ZrX
monohalide
hydrides
structures.
Hydride
increase in the distance between the atoms
zirconium
are
presumed
atoms
to
[79].
occupy
X-ray
and
the Crv'
spectra of ZrXHc*a, ZrXH (X = Cl or Br), and ZrH,.,, indicate an
appreciable amount of Zr-H covalency
[80].
Trends in XPES data for zirconium, ZrCl,
(n = l-4), ZrBr, ZrxH,
or Br; x = 0.5 or l), and ZrClOo,, have been reviewed. the zirconium
ZrCl
[78].
powder
and
(12) do not occur between ZICL and
3412 level
oxidation
state
except
displaced
to higher
exhibits
a regular
for ZrCl, and
binding
energy by
(X = CJ
The binding energy of
increase with
increasing
ZrCl,, where
the binding
ca. 1.3 eV.
The break
formal
energies
are
in the trend,
t.ris(%,2’-hiI,vricline)
The [Fl(hipy)3] by
and
rr4uction
contain
a
C’”I 0l~7Fd,
[M(phm)3] of
or
HfVl,
stnirheiomet,ric
Hetwohimet.al1
ir
h?; react inn of
st.ruct.lrre
of
.wnnit.ixx=,
prepared
the
of‘ the
in
a met.a 1-rwt.al
with Iwnd
type
t.hese
of
.(25)
80% yield that.
arp
dark
[82].
[(cp)27i%r~((.~~)z(~p)
compunds
[(cy))2(MF131:O)7rR11(Cc))2(cy))]
ca.
solutions
rc>mptpses
and diamagnetic
one equivalent. in
in
t.hf
These
Ijgand.
Ru; N = COle3 or Me, r+hen M = Fe)
[ (cp) ,%r(‘tX]
nf
ha.x+e ken
ncxxlium amalgam
monomeric,
complesen
q
Hf),
of
compl eses ,
t.ris( 1, lo-phennnthroline)
vit.h
;unolInt
air
CX74est or Me, when ?I
prcwww
(Fl = %r or
%
extremely
and
have ken
]
(X = r-1,
synthesized
li[(~p]M(C0)~]
in thf.
was confirmed
by the
{r(%r-Rut
q
The X-ray
2.910(I)
A;
CP
(25) r(%r-0)
= 1.910(4) The
iI; Zr-6-C
compl exes
[ (cp) W(rCC1611,Ple-4) ((‘0) z ] and relat.i.vel
y inert
= 169.6
-1 [X3].
[(~I),M(CO)~I
in
to I wne
(M at. 55-70
bimet.n I I i.c compwnds
=
Ti
Zr)
or
‘(“ t,n give
the
[ (cp)$l(~-CC,H,Me-4)
rf?,xA.
thermally
with stable
(c~-C~~)W(C~)(Cp) ]
C,H,Me-4 I
1. 2. 3. 3. 5. 6. 7.
x. 0. 10. 11. 12, 13
.
14 . 15. Iti. 17. 1X.
155 19.
Ii.
Khera
1:1
(19H:l)
N .li.
?kta
I-Ckg.
.j.li.
Iiaushj
F1. iihera, 13
f‘hem.,
Sharma,
rN~ta /-Org.
n.
13
23. 21.
iFLSW, Div. Kh.
n.1..
?lntnv Nikitina
29).
1j.I..
nnd
N.K.
Metal-Org.
Jia\lshi k,
.‘$nfh.
Rw~ct.
lnorg’.
Karlshi
Spth.
React.
fnnrg.
Chem. ,
k,
10.59.
N.K.
Kaushi
Iia;Fillshik,
k,
J.
Indian
YIP. and
(1983)
Rogar~hw~,
P.
and ().,A. Mi khai
31 ( 1482)
1429.
fbainina,
%.S.
R7s.s.
Zalkina,
liooro’.
( 1983) 399.
1 n\;a,
Klemenkova,
J.
i
Snc.,
Ru.1Z _ Acad. Sci .
B.V.
Iokshin,
T.D.
, &II I. ,Jr;ld.Sri. LX-Z', RPFIC~..Inorg. ~~Iet.~I-Org.
Inorg.
fhem., 27 ( 1982) (1983)
[ihim., 9
IO.57
1X0-1.
[C’hem.
1487151.
I..M.
Pnmi-Knshits,
Soxi nova,
0.4.
Chwn. 113
?\onatsh. fhpm.,
Xinarheva,
E.V.
and
9!4
Ahstr.,
34 * 35 .
rnorg.
T , %hdannv, and P.1.‘. Petrn\-ski .+i . , 3% (lwx! f)iI..i%rm. 126.5. S , S:*xena , \-.P. Singh, and A.!<. I?ai, .‘?.rnth. c-hem., I:< (1983) 855. S.D.
31 . 32. :i:<.
A?eart.
S,
27. 2x ,
30.
and
.Sr-i .,
Minachwa,
N i kol AI~GX,
26.
Sodhi
Cbrm.
N.K.
(1983)
13. Jihw-a
, G.S.
and
Khera,
I’hc=m.,
60 (lW3) 209. A.[<. Sharma and N .I\. PI. Kh. li.Pl. JIrai nina, M.
.S.r-nth.
( 1983) :1X1 .
22.
2.5,
k,
357.
Sharma,
A.l\. ‘21 9
and
J.
Dikarewa, .StnxV.
V.
1-a.
K~tznetsov,
I,..!?.
Fomenko,
and
M.A.
76.5.
Them., 23 (1982)
>lc~l ‘ni iron-a, II. K. F:f i mov, S. K, Vasi n, and V. .A. Fledvedev, Russ. J. I-YI.I:~, ('hem., 57 (19,83) 991. S. Singh, M. I+di, and JI. V:erma, .I. F’lrlorine Chem., 20 (1982) 107.. (1. ‘I’hwalt, and k’. laswr, Z. rVatruTorsrh., 7’eil R, 38 (1983) 1501. 4 .V. Dudi n, V. P. Baharca, and V.Va JZosolovski i , RIJSS. J. Tnorg. Chem. , 2x ( 1w:4j 950. I[. T
(‘hem. ,
rnorg.
36. 37.
R.K.
hgar-wal
I?.K.
,Agarwal
98 .
Yu. \-;I.
Thrrmwh
im. Khar
(1982)
39 .
P.E.
Riley,
10.
t4.F:.
Silver,
41.
M.A.
Si Iver,
42.
S . Jillmar,
33. ,l4.
W.1,.
Stctffen,
4.H.
nr~~der,
Thermochim. Arta, 63 (1983)
PI. Srivastava, l3.S. Ada, 61 (1983) 235. i t.onov , M. M, Wkhi t., K.
Ah{]-l%wi,
and
ICisenst.ein,
and
R.C.
FRY,
and
S.F.
A.R.
113.
Srivastava,
J+Lr=vski
i,
RIISS. J. Tnorg.
1i.N. Raymond, and R.C. Fay,
rnn0r.g.
(Xem.,
Inorg.
22
(1983)
3940.
Chem., 22 (1983) 759.
Or:g,wwm~tailirs, 2 (1983) 44 lialshik, Russ. J. Tnorg. Chem.,
N.K.
and
Stxlhi,
G.S.
and
Tyagi,
1109.
0.
(l!w:{)
1582.
,
(1983)
rhrm., 28
2K
27
;md S.C. &~nto~i,
196.
H.Ji. R,.C:.
and
Chlln, Fay,
D.F.
K.C.
Fay,
Lewis,
Tnorg.
and
A.A.
17
Chem.,
Sayl.er,
(1978)
3398.
J. Am. Chem. SOC.,
9x (1!476) 6932. 45.
4.Ji. 13
Sharma (1983)
A.F’.
I,indmark
S. I,.
Haw+horne,
Ts.
R.
f&lss.
49.
and
Ts.
and
Ka~rshi k,
R.C.
A.H.
Knnrmova, J.
H.
N.K.
S.ynth. React.
Tnorg. Metal-Org.
Chem.,
101. Fay,
lnorg.
Rruder,
and
A .Yu. Tsivadzp,
22
Chem., R.C.
Fay,
A.N.
Smirnov,
(1983)
Tnorg.
2000. C’bem.,
and
S.
A.
22 Ku&i
3363.
(1983) tskaya,
I'nnrg. Chum., 2X (1983) 515.
Konunova
and
S.A.
Kudritskaya,
Russ.
dJ. lnnrg. Them.,
28 (19X3) 437. 50. 51.
R.K. AgarwaL, B.S. 771ef7nodlim. .4cta,
55 52.
Srivantava,
A.K.
(19X2)
Acta.,
53 *
M.S.
54.
S.
55
M.
A.N.
(1982)
Novakovski
Gambarot,t,a,
Chem.,
22
M. Srivastava,
and
A.Ji.
Srivastava,
(1983) 241. Srivastava,
a.nd R.K.
.Agarwal,
Croat. Chem. .4ct_,
429.
(‘hopa,
J.R.
Tyagi, 61
( 1983
Pander,
S.P.
Sharma,
and
R.K.
Agarwal,
Croat.
['hem.
283. i
and
V.R.
C‘. Floriani,
)
2029.
Timot’eeva,
A.
Chiesi-Vi
J.
Cen.
(‘hem.
l.la,
and
52 Guastini,
I.!‘+X,
C.
(1982) 2136. 1nnor.g.
156
56 .
59. 60. 61.
67. 68. 69. 70. 71.
72.
7tj. 77.
80. 81.
82. 83 .
131
I KI1xmY:‘r
131
2.1
I ON ..............................
Zirconium( IV) and hafnium( compleses
IV) compounds
.............
2.1.1.
Halide
2.1.2
C'ompleyes wi th O-donor
2.1.3
mmpkses
2.1.3
Complexes
N-donor
2.3.5
('ompleues with &donor
2.1.6
Hydride and hornhydride complexes
, ............
, ...
1i gands
133
..............
139
with
ligands
........
Iigands
....
2.3
Zircnnillm(T) rnmpunds
2.4
%ircvnirrm(O)
2.5
Cnmp\lnds
.......
, ....
compounds bonds
hafnium. The solid-state organometallic
OOlO-8545/87/$09.10
, ....
of
in
h .. , ...
.....
series,
t.he coordination
chemistry
compoilnds are
only
0 Elsevier Science Publishers B.V.
this
cbemjstry
of these elements in~l,~ded
150
, ...
152
, ........
.............
this
149 149
.........
, ....
previo1ls practice treatment
142
............
, ......
and hafnilxm(O)
wit.h metal-met;tl
. .....
REFI?RENCCE~ ......................
and
132
with S-donor ligands
%irronilrm(TTI) and h.qfnilrm(TJl)complznds
Following
, ...
..............
2.2
comprehen.sjve
132
when
153
, ...
153
, ...
154
review of
attempts
zirconium
and
is treated selectively, the
compunds
contain
132
The
reaction
acetic
acid
nn
molar
the
CsHfF5
is
[Il.
bepn
atom
stretching
f 1 uoroz
fying
doderxhedra
(M”
glasses
contains
dimer {r(Zr-F
also
that
an
network in
which terminal)
The
oxide
the
earlier
has
of
q
the
[CU,(H,O),,]~~, bonds.
2.048-2.107
flunride
A;
Ph%r6Fz&
radial
[Zr,F,4]6-
[Zr2F14]
r-(Zr-F consists
of
ion
fo~~nci /.rF,
!la%rFB
[a].
(15-.5X0 sit.es strA>-
Ii) [51.
[ 7 1 r>t
The
s t I’IKY~IU-C=
that,
are
linked
i s a pentros>mmet
~(xnmon
and
~
proTons
= 2.171, a
o-f
t,hnse
infqrrivalent.
ion
a
in
iOn analyses
ions
fi-
bridging)
t.o
llrn in
di t’fract
t,he
share
atom
Im
measurements
a neutron
and
metal guide
of’ a-w&e-share?
dist.rihllt
of
for-
the Raman spctra
zi rmni
two
for
a rpl iable
t*eat\lres
for
The
symmetric
da.ta as
st~xli ed
prpsPnt
Raman
z i rc>oni
chains
ncrupy
anti prisms
square
similar
7~rr-oni11m
ively.
are nf
son
the
of
locat,ion
The
*H,O
phases
Iwpn
r-espct
llt,i 1 i zed
cnrrPIatiorr
IS],
the
of
) have
structural he
ronment,
X-rap
anhydro~~s (‘sHfF,
cii t’fprent.
Ph
How~\~?r,
hit.
atoms
study
identified
%rFe
table
anglil.ar
hafnilun
S-ray
hydrogen
two
with
or
Sr,
c:ont.ains rnvi
per-t~~r&d
indicat,e
rshi
that
six
(‘ompari
cannot.
Ph)
c:onsist.ent
[CU(H~O)~]*+,
dense
or
M”%rF6
of
mod i t’icxtions
~~nknown st.ruct,ure.
Sr, of
differential
Cu, (%rF7) z lRH,O a
form
dqxnding
hydrate,
sp+xt.roscopy,
number
An eight-cnnrdinate
is
Fo1 lowing
of
synthesis the
environment
CM” = Ha,
avai
coordination
= Ha,
I ine
[ :I] f
Time
Us( Zr-F)
romp1 exes
crystal
NH,Hf2F,
and
t.hat,
;inhydmlIs
[Z],
SrZrF,,
v,(Zr-F)
in
CsZfHfF6],
pol~morphhism;
Rxna.n
and
to
yield
high-t,emprrat.llre
Ba%rF,
the
M”%rFs
the
and
indicates
irconat~3
vitreous
on
for
and
or
approar.r-h
diffraction
\l”%rF’,
fluoride
rsHfFS
c~oordinat.i.on
analysis
freqtiencies
florozirconates ident.i
powder and
iow-
as we1 1 as
This
compLex
vitreolls
thermal that
caesium
acp~e:nt~s preparations
X-ray
and
and either
rompnents.
properties
I ine
fluoride
compounds,
reveals
by
sllggcst.
PhZrF,,
PWrF,
the
K,HfF,
thermal
TV)
soLid
since
identified
DT4 data
for
of
of
ng
differ~nt,ial
for
two
ratio
crystal
in
hafnium(
convenient
The
by
yields
fbati
have
of
s
polyhrctral
2.185
threp-dimensional
by ric-5 +.p
k]. framework
133 of ZrF,C sq~~are sntiprisms, which enclose two kinds of cavities. cuboctahedral
city-itiescontain
cavities rontain
one
atom,
GihiLe the
pressures of Cs,MC1,
(M = 7.r or Hf)
(equation
have been measured, and thermodynami.c parameters for decomposition
Cs,MCl,(s or I)
solid
compounds
vapur
ha.ve been
pressures.
been reported. respectively), reaction
of
ZrCI,.2hH,,
M
derived
Na$fCl,
gaseous ZrClN,
from
the
X-ray powder ptterns
K,HfCl, and Cs$fCle
but
with
and NH,Cl at
temperature
of M',HfCl,
smmonia
yields
ZrsN.,, and NH&l ZrN,
1300-1400 'C.
(.A- =
thinsemioarbazone,
ZrC1,.2NH, ZrClN,
t.he
[9].
at
a
=
NH,CI,
IO.13
i
and
The
300 'C;
ZrN,,
at 800-960 'C; ZrN,
1.28-1.12),
ZrCl,~2NHs has a cubic unit. cell with
Zirconium(TV) chloride acetone
of
Na, K, or Cs) have
q
350-700 'C; ZrC1,,2NH,,
1000-1050 'I?; and
depndence
(a = 15.99, c = 13.21 k)
and NH,Cl at 750 "C; ZrClN, ZrN, at
(M'
(11
are cubic (a = 10.036(3) and 10.394(4) A,
is tetragonal
ZrCl,
of the
2CsCl(s or 1) + MCl,($)
and
MT,Cl
larger
112 t tiJ-coordinated lesd atoms [8].
Eq~lilibril~mdecomposition
(l)}
'extra' fluorine
The smaller,
Zr3N4,
ZrsN,, HCl
at
[lo].
forms solid I:1 adducts with aminop_yrine (1) and Infrared
Me,C=tWHCSNH,.
spectra
indicate
that
Me
M N
/
\N
I Me2N
'Ph %i
0
(1) both ligands are bidet-&ate. carbonyl.
oxygen
atom
and
t,hiosemicarbaxone coordinates
Aminopyrine coordinates the
to zirconium through the
djmethylamino-nitrogen
atom
[ll],
while
throllgh sillfur and the azomethine nitrogen atom
L121.
Vibrational
spectra
of
ZrCCI, *SH,O and
its deuteriated
analogue
have
and
2198 280490
2180
rm-I,
cm-l
{eqllation
[ 14
(3))
hands
l’( Zr07r)
].
reaction
The
yields
the
at of
oy-o-bridged
3[ ((Me,Si
[ ( I(MF~~S~.)~N]~Z~MF!]~O]
605 and [ ((Me,Si
584 rm-l
complex
[ ((Me,Si
wi t,h
ln
(2).
),N),ZrMe,]
t
, and v(%r-(‘I
)ZN}Z%rMe2]
the
)
hands
carbon
at.
monns-idr
, rwmpo~xxl
r-rystal
+ 2rx)
)ZN}2%r(0(~(Me)=(iFlez)
(Me)
]
(2) is
(2)
rnntrasymmetrir:
r(%r-N) hy
= 2.081
exposing
hours,
a
has
as
174.1(312
0.001
st.irred
a,
z-( Zr-0)
and
benzene
ox-o-bridged
%r-b-Zr soIut.ion
struCt,ure
=
1 .%O( 180”
q
of wit.h
1)
i\,
[lFt].
=
2.225(3)
[ { (cp)2ZrYej,0],
[ (cp)27,rMe2] I-(%-0)
i-t zr--(’ )
=
to 1 .Y3R(
the
,;,
nht;linFul for
air
I ) ,i and
sixteen
Zr-i)-%r
=
[16].
Solllbi HO(XMP,)
f
wi t.h
I i ty
syst.ems
A1.Zr(CCHMe2),,
measurements have
hIIt, failed
nonfi to
in
the
A1(~~Me2)3-Zr(rH~le~)4-T.
rmed
the
exi stance
provide
evidrn0=
for
nf
t.he
(I.
=
bimetallic
.~I)2%r(WIDI~2)Io
thf alkoside
LIT].
or
135 The vo I at.i I i t2; and thwma I decnmposi t,i on of
[M ( t.f’RCRlP)4 ] ) and
[M(CICRC)4I,
tkYn Rtlldic=vl hy VOlkO\ et RI. A variety or h7.a~; of
and
A similar
his(r\5-inden>-l
) have
t,he
has
and
[21,22],
and
= MP,
the
proposed
on
are
of
are
soIut.ions
the
correspnnding deri vat.i vest
)
[(175-Cg~i7)(~s-_(~4114N)Zr(a~ar)
j(S2CNRR’]
[(cp)zzr(dik)](S,CY)K]
= acac
A3 I of
IH and
bidentat.e
= a,-~
t.hese
(dik
complexes
coordination
abIt
ItI NMH spwt.ra, and
t,he
behave
or 1: 1
as
zi rct-mi urn has
which
show
dil,hincarbamat~
that
and
t.he
xant.hat.e
urwonrd i na t,ed .
1 ,3-l)i ketonate[(cp)Pl(dik)2(N0,)] have
[23].
aq\wous
t.n synt,hesize
) (~5-pyrrolpl
Wtrahedra1
hasi s
1 igands
1 ,3-di.1retnnat.e groups
the
have
Hf)
N, Wdi a I kyl di thi ocarbamate
sndiwn
used
salt.n,
Cllble,)
in nit mbenxPne.
elPrtrolyten been
or
at,e
hwn
and
alkplsanthate
Et,
by mixing
prelwred
(Q5-indenyl
[(~5-r91{7)2%r(aC;Ir)][SZCh~H’] hZRC ; R
chelates
(dik
[(n~)~~r(~ik)][S,rNRR']
been
appropri
proredure
)
ket,onats
lM(r~F,(-~F‘,(:F,~~Y)(Hc'tw~l-l,),] (M = Zr or
nt’ t.he typ
or aryl
[tcp)2%r(dik)]C’t
[ 19,201.
1,3-di
[18].
of’ complexes
R.,R’ = R I kyl
the
hen
a.nd and
prepared
ty
are
giyw
romp1 ews
[(cTp)M(riik)(NO,),]
(M = Zr nr Hf;
rcartion
acid
ha,f’ni IITI 1 ( 3-d i kc+.onat es rwrt.ions
ni tratewnt.aining
in
in
of
nitrir
dirhlornmet
fqi~~l ions
1 (cp)M(dt~=.m)~Jt HN$
(-1)
bane and
with
or
of dih
t,he
= acar
appropriate
or dhzm)
zirconium
1 ,‘&dirhloroethane.
(5).
Reactions
of
types
Typica
I
[(cp)M(dik)$l]
[ (~~~)M(dhxm)Z(N03)] t dhzmH
------+
or
(4)
20 *t:
[ (cp)M(dhxm)z(N03) with
nit,ric
arid
to
lrrl
[ (rp)Y(dhxm)2C1
I t IRXJ, the
formation
-
]
(dhzmll or
t,n
IWenzw)
1 ,3-rli ketonate and
t.wn nr three
(NO,),] prnd~vts
+ dbzmH (eq~~+tion
t (rp)Wl,(NO,)~4H,O
(5) (6)
(6)
‘r
Hvo, .-----+ -35 -r:
r~=~3~~~rtwl
of
[(“p)M(dhzm)2(~(~3)]
-35
(M = Zr or Ilf)
1(cp)Pl(dlzm)
----
[(r?p)Zr(ac~c)z(Nna)] t
cnmplcx~s
tri4.hylamine
t
I (cp)%r(acar)(NO,),l
(rp)Zr(‘12(N03).31120
i Ipnn
(quation
(‘i)
t.reR t men1 (8) I.
wi t.h
1 ,3-rli ket.one
'l'he[(cp)M(dik)2(N03)]
136
(cp)ZrC1z(NOs)~4H,0
t 2dikH t PEtaN
(8)
[(cp)Zr(dik)z(NO,)l
-----+
+ 2[Et,NH]Cl+ 3H,O
and
TR
tetrahydrofuran. bidentate
indicate
speotra
and suggest that the nitrate
non-electrolytes
essentially
are
complexes
](cp)M(dik)(NO,)zl
that
the
in
ligands
l,%diketonate
Iigands are probably hidentate
are
as well
124,253. Heterocyclic (dik
is
the
tetrakis(1,3-diketonates)
anion
of
the
tyyx, Zr(dik)n(~HMez)s_n
4-acyl-3-methyl-I-phenyl-2-pyrazol-5-one
of
(3)
and
R Me
-3
OF
N/ \ ,t
'N
I
Ph
(3; R = Me, Et, ph, 3-ClC,H,)
II q
1, 2, 3, or 4} have been prepared by reaction of stoicheiometric
of
the
pyrazolone
complexes
are
composition complexes analogues,
and
Zr(CYCHMe2),~HOCHMe2
monomeric
in
boiling
Zr(dik)(CCHMez)a, exchange and
alkoxide
they
ligands with
or
NH4)
are
&Hf(SO,),(H,O),, sulfates
have
complex eight
anions oxygen
investigated
in which atoms
from
2.283 A), two monodentate
Me&OH
two
of
[271.
[28], and
hafnium
atom
bidentate
sulfate
amounts These
reflux. the
compounds
of
The Zr(dik),(CCHMe2)4_n
yielding
Zr(dik),(OCMea)+_,
giving
the
insertion
(n = 1, 2, or 3) [26].
the
ligands
systems type
(M = Na, K, Rb,
M,Hf(SC4)atH,0),,
IR spectra of the sodium hafnium the
has been determined the
at
for
isocyanate
sulfates
complex
[NH,]4[Hf(S0,),(H,0)z]~ZH~0
except
formed in the HfOz-M,SO,-Hz0
and MsHf(SO,),(H,C),
been
with
phenyl
products, Zr(dik),jNPhC:(0)OCHMez),_,
cs,
benzene,
benzene
which tend to dimerize.
react
Among the compounds
in
X-ray [29].
crystal
This compound
is dodecahedrally
sulfate
structure
(r(Hf-0)
q
contains
coordinated
1igand.s tr(Hf-0)
of
=
by
2.223,
2.067 A, and two water
137 molecules
(r(Hf-0) = 2.196 A).
edges, and the monodentate
The bidentate
sulfate
ligands
ligands span the dcdecahedral
and water molecules
a
occupy the B
sites. Standard ra~orimetric
enthalpies
measurements
Hf(SO,),-4H,O
of
formation
for
at
Hf(SO,),
298.15 K
(A%
fluorosulfates,
Zr(SO,F),,
and Zr(OzCEle)3(SOsF) have been synthesized Zr(OZCCF3),,
spectra,
compounds
anhydrous
the fluorosulfate and
COtlIpOUll&
good
by
complex
the
ZrCK&,
(Csv
Lewis
or
mol-l)
by reaction of fluorosulfuric Zr(O,CMe),.
sytmnetry) in
acids
and
reaction
has a
On
form
sulfonato-complex of
[(~p)~ZrCl,]
five-coordinate
bent
basis
by and
coordination
with
IR
All
complexes
four with
[31].
AgCFsSO,
metallocene
acid
of
in the first three
[(cp)2Zr(CF,S0,),(thf)]
Cl3 C23
(4)
the
Zr(O&Pie)a(SOaF).
oxide, pyridine, and 2,2'-bipyridine
The trifluoromethane prepared
determined
ZTYO(SO,F)~, Zr(0,CMe),(S0,F)2
ligands appear to be bidentate
tridentate
are
triphenylphosphine
This
been
have
-2230.1 f 3.4 kJ
(AH+ = -3492.8 + 3.3 kJ mol-l) [30].
Zirconium(IV)
with
=
has been
in tetrahydrofuran.
structure
(4) in which
there
Xi-(011 SC,1ut
139 (b)
complexes of the typF? IZrOX,L,] (X = Cl, Br,
aromatic amine &oxide
N(:S,
or
~Zrol,,]
and
NOs)
2,6_rlimpthylpyritline mono-+oxidej)
(c)
[C10,j2
&oxide,
(I,
=
or
HphenNO
of
the
pyridine
N-oxide,
lI,lO-~henanthroline
[Z17];
dimethylmrthanamirie M(So,),(dmf),,
compleses
MOS04(dmfl(HzO),
WI=
i%Clz(dmf)z(HzO)z,
and MO(CIII)(NO,)(dmf) (M = Zr or Hf)
[38].
The been
t,etrakis(l-oxo-2-pyridonat.o)- compLes,
reported
in connection
nine-coordinate
2. I .3
c’omp
thori.llmcompound,
I m-es
Sevrral
wi th
papers
the structure and
and
five-coordinate
S -&nor
bent
an
X-ray
structural
study
of
the
has
related
[Th(CsH,NO,),(H,I))].2H,O 1391.
1 igands
have appeared
molerular
monothiocarbamate
(r(Zr-centroid
with
LZr(C,H,NO,),]-CH(71,,
during
the past
rearrangements
complexes. metallocene
cp) = 2.216, 2.222 A;
An
of
zirconium(W)
X-ray
structure
year which
(5)
study for
has
shed
light on
dithiocarbamate estahl.ished
a
[(cp),ZrCl(S,CNQ.)l
(centroid cp)-?r-centroid
cp) = 129.4').
(5) The zirconium
atom, chlorine
atom, and the two sulfur atoms of the hidentate
140
1igand
di thiocarbamate ~rpendicular t/he
to
two
cmwling cnord
in
txmd
length
.i};
0.3
kJ
mechanism
of
dithiocarbamate equi
Ii brium
probed
by
similar
rxtended
for
1ong
(r(Zr-C*l thP
of “(1
f
the
im-r>lvp
pri nr
possibility
mnlw~~lar
monothi
met,al locene
t, i on
of
orbital
Zr-S2
structure
(6)
terminal
,
A($(
28 thr
t,he
a.n;llogo,~s (‘)
2.5
= 67.7
K-l.
l’htin
the> Zr-8,
bond.
ruptllrP
have
bond
bond
aft’nrtlpil
C’L-FU’ bond
of
.\; atrd
%r-S,
thy
.J mnl-l
thP ThP bcn
[ilO],
1 (cp)zZri‘l
with
%r-(‘I
The
s-1;
Calculations
ocarhamato-comples
lateral
NFN nt.\lriy has
f
of
2.5.56(Z)
=
in
al-Kwt ruptllre
thp
grolaps
8.6 = -4
Iy
mPal1RP 0 f
to
)
longest.
near
thf> crnt.roids
bonds
MHz ‘II
A.@ rota
and
11’) cornpI++;,
methyl
is
that
I iganris +
the
A Xl0
eyrhange /i( 25
may
atom
grolip,
zi rcwniwn( 4).
involvw
and
HG-kel
xircnnillm
are
a
pfane
I npw tadi eng I
67+8kJmol-1;
and
analogous bent,
for
process
geomptry
The
dist,ancen
=
1igand
mi rror
Iy
these
rompleri:
t.his
the
1musi1al
dat.a
AF8
by
n5 +yr
= 2.6:15(2)
kinetic
mol-I;
quasi
nhservrd
(r(Zr-S1)
L(cp)2Zr(‘l(S,CNMe,)] f
a
cwordinat.ion
yet
normal
following
defined
at, Lwhed
sites
I engths
is
in
%rCIS,C’,,
= 2.723(2)
r(iY-S2)
the
plans
~a.1 I y
the
i na t i on
Zr-S
the
symmet,ri
lie
(SWNMP~)
has
I
monothifxarhamate
a
1 igand
(61 oriented
so
as
congested,
lateral
congested,
interior
r( Zr-0) 2.236 76.1
= 2; .;
I(cp),ZrC1zI
to
(centroid
with
the
coordination
2.249(4)
Cl-B-43
place
adjarw~t.
i;
I-( 7r-S )
138.1 anhydrous
‘1.
oxygen
site
site
cp-l.r-cwt.roid =
smiler and
t-o the q
the
larger
chlorine
2.641(Z) cp)
atom
=
128.5
.;
NafSOCNMe,)
in
hoi ling
S-Zr-0 was
atom
{r(Zr-_(.:I
r( Zr-rent
[(cg)*~r(:L(SO(,‘NMe,)]
sterirally
sulfur
atom
,i;
t.he
in
roi d =
)
in
preparw1
the
= 2.5.X)( cp)
62.0
dichlorometh8nP
more 1~s~ 2)
2.2:30,
=
~; Cl-ir-S by
react, l-11
.I;
1.
i on
r of
141 Hafnium(
IV)
[ (cp) w ( s,wm
dit,hiorarbamat,es
J ) 3 1 I rm 1 = Et, by
been sgnthpni 74 molar
Al 1
ratio.
solution,
and
of
of
these
rF? sppctra
five-cnordi nFtte
met8
[
t-xvt
[ ( cp )M( s,(‘:me, ) 3 ]
(M
t.he
lloc~~e
(cp)Hf(S2CYRR’)3]
[
Ti
j
dithiocarbamate
like
are
Zr)
in 1: 1 CT 1:3
non-electrolytes
[(cp)ZHfCl(S,CNR3?')
structrlres
or
Na (9,CNRR
in
ligands
have
[(cp)2Zr(ll(S,CNEt,,)]
pen tagona
143,441.
hi
i
are
complexes
[40],
pyramidal
Analogous
Like
bis(fLuorenyl)-
-~alkg‘l~~arrt.~rato-cnmpt~ses, [(17s-(:13~9)z~~1(~2~)~)i (n = Me, ha\-e
and
(cp),HfCl(SZCNE?R')I
monomeric
the
compnlrds
=
and
are
s11ggest. that
PrPs\~mabl y,
t.he
[ (cp) ,IIfCl 2]
complexes
hirirntat.e [42].
and
types
I(-r,H+Me; H, ~yrIo-(:~H,; or II, cycle-C,H13) have
waction
of
t.he
Et,
0r
CHMe,)
been preparecj by reaction of equimolar amounts of [(Q~-C,,H~),Z~C~,J and in
K[S,MR]
dimethosyethane
I,ow-temperature i
equally
ntenne
septets,
[15].
lflNMR
isopropyl
attributable
to
spectra
methyl a
of
doublets
ligand
[%r(S2CN(CHMe,),],] and
two
conformation
equally
(7)
in
exhibit
intense
which
the
two
methine met.hine
Zf
4
(7)
protons of the inequivalent Ligand.
4t
higher
coalesce
to
a
isopropyl groups are located in the plane of the
temperatures,
single
doublet
the
methyl
doubLets
a
single
septet,
and
hindered. rotation about the C-N single bonds.
= -39 f 5 J mol'l deg-I.
of ZrCl, with
Na(S,CN(CHMe,),)
Low-temperature [Zr(S@XMe2)4] consistent (8).
methine
respectively,
[Zr{S2CN(CHMez)2),J was prepred
Variable
temperature
to
by the reaction
in the presence of triethyl phosphite [461. spectra
'H NMR
the smtrum
due
= 45 & 1 kJ mol‘l and
of
the
monothiocarbsmato-complex
can be interpreted in terms of four overlapping
with
septets
Rate constants for this process
range from 20 s-l at -25.0 'C to 670 s-l at 21.0 'CT;A# A$
and
expected lH
NMR
for the Czv dodecahedra spectra
indicate
the
methyl peaks, stereoisomer
presence
of
two
142
(8) dist,innt
kinetic
processes:
rearrangement., (b)
Coa I.escence deg-l)
Ati=
f
AG”(78.2
process
douhl e
bond
1; ‘C)
for AS*
the -34
q
82.7
q
L’I’P f
i
and analogous
[M(S2CNR2)_,J
rearrangement,
mecyhani sm for
thiourra
in
,Cbond~d
thiourea
dimeric The
moleclllr
is
rconium(
= pyridine,
bot.h
Cal 0rimetri.c
at,t.ached
‘Z,tSdimethylpyridine,
or
Zr)
t,o
to
t.hr
of
in+ract
IV)
with
comp
Z-methglpyridine, q~jnoline,
the
I ex~?s
C--h:
1 :2
complex
with
and
[‘vi
0.2;
= 7P.2;
The
15.
or
f
greatzer
(S(X’YMe, ) 4 J a
p~lytcpal
with
metal
t.hiollrra
c,hloride
and
1 :1 addrrr~ts c>ontain
ng
has
oh lorine
bepn that
al.oms;
srlggestrd on
I y one
a
l.181. t h i ourpa
adrhct.s ; t hf> st~c~onc-l I h iolllTc’:x
VIR
hydrogen
Whet.erocyc
or
‘/;,
HfCl,
the
hri&i
2-aminopyridine, W(bipy),
H’I’P are:
wi th
of’ t.he
i ndi
the
47.1
[ 47 J .
t,hat and
mol-’
=
suggests
ZrCl,
indirate
in
f
son
complexes
amnunt,s
measllrements metal
qi
q
process
terminal
C)
the
rompari
I((~~2Eu’)21‘SJC1311~12M(:13(S(:(~M2)2}] and
appe_ars
Oxozi
Ti
for
A,+
in
stoir>heiometric
and
the
(kJ
A(;5(-53.5
values
9Yk5;
IR spectra
1igands
-53.5;
1 and 2: 1 adduc:ts
mixing
acetate.
st,ruct,ure
IF? spectra
molecule
(L
ethyl
=
t he met a 1-centered
1: by
=
=
about
parameters
activation
‘&
(%r(SOC’NMe2)4] (M
rotat.ion
1 igand.
and
Al?=
of
Moisture-sensit.ive prepared
the
Corresmnding
0.5;
rigidity
been
mcta I -mw t,~r~d
invn1vin.g
involving
(HP)
are:
I‘i .
stereochemical
have
in
(“C)
t,empwatwes
J mol-1
(I,‘I’P)
and
a high-temperat,ure partdial
40
process
low-temperature
a
(a)
H(phen);
Lic
ho&s
[‘18,49].
Iigands,
%rrX,[,
2,4-dimrt.h~~p;vritline, II = 4 r;hpn
\
J (‘1,
b,
143 L
I
ot
n
r’lc!,;
or
t hew
prch
2 when X = NO,,
q
arc?
complnds
Iorate
or
non-e
dw-iVat imps,
NW),
1 ect
which
rol
have i n
yt.es
h&we
heen prepared
as
1 :2
ni
in methanol .
t.rohenzf=ne
except
eIectm1y-t.e~.
Al I the
for
Infrared
spctra
indiPatr5:
t ht=
(a)
:ShPterocqr
I ir
hPt Pro-ni t rc-xgen Sami nqyridine
atom,
and
the perrh 1orat P w)rnp,Iuxk
f (‘)
thts n i t rat e I igands
(11)
I tar NCS- 1 igands
+~oxi rcon
1 i g;rbrls
i II
l\:)
i rrm(
are
rest-ts
or
(‘IO,-
in
a variety
tri le,
bipy,
s t IKJi +--d ( Xi ] ,
anfi
z i rconi I em-hydrogen
I)iazna i ka.ws
((cp)2%r(l~)~‘l rorikain
I,,
$-N,
H’.$=N=N
respect
1ai.f~rit
C.1, Hr,
or
2
_I )‘I-“,
of 1;
n
2.12(Z)
( i-l XI--M+ ) r’(7.r~Cl i
A
= q
i
ot‘ thr
irit-li(‘atP
1- )
l’he
=
hnnd
.i
in
(lo),
in
(12))
is
1,
also
d~lo~alizat~ion
t.hene
int.a
or
other
(lo), lateral
=
2.37(l)
and
metal locsncn and
or
that (10)).
that
t,he
Zr-N
2.21(l)
A in
hond (ll),
coordinat~ian i
lengthened
‘I’he X-ray
6),
has
CH,Ph)
(9)
interi
or
zirconium-carbon
Me
=
4,
compundn
indicat.e
ji in
I igand.
3,
and (12)
2.103(9)
si,grrif’icantly
2,
t.he correswnding
(wpr8tions t:he
t.hp
of
bent
(11))
r(%.r-(lli$h)
hydrazonatc>,( 1-j
ll-f+l~~tt-ot~j~
(H
t ban
t,o
that.
zirconium(lV),
q
insert
ligands
(10) ,
I ongcxr r(Zr--NR)
(12)].
2.549(51
II~-attac~ynent stlidiw
in
2.357(6)
WzKt)
five-rnordinab
nt’ comprrnds
i;
t ion
[ ( c~)~~.I-I?~]
pielding
is
.25-2.28:1
decompni
= Ph or of
hydraznnatn(
urw bond
I
1, ( r-(%r-WI? and
ivcly,
!V’-bonr~ed
\-VI\- cy)-st R I ntnrt
(H
bonds
These
indicate
[ .52] .
7,~‘ I 4 rci t h ‘i( GII,NHNH, or
bm
pyridine,
OT- phen).
(X
-l’he t herma I
b&donor
%rO(NCSe),L
and IR. spert,ra
~~~~‘,~I,NI~~.ll,],~-/r~:I,_,~2~~YH~~FI,’,),] hyClra7j np hy-lrc>r~hI orid+.
and
ZrC,( txSe) zL2
and
romp1 P\;PS q
0-
tw
RTP r~htalned
thrt rwwt.i on of
at.om [SO,51 1,
(Hu,Sn ) ,O,
N, :V-dioxide,
rthaneni
S\lklst i tilted-ph+>nyl hydrai-idr,( 1-) from
t.he
of
i ens;
of
the
of
pheny-1 hydrazine)
2,2-bipyridine ytes
atom
the nitrogen
Ph,W,
ww t Ri n &T-bonded t h i or’yanat P 1 i gands
t.by
with
,WOXidP,
hydraz i ne,
non-p I wt.rol
through
compl wcs
p?ri d i np
(1, = -I-aminnentipyrine,
amino-nitrogen
hidnni.at,e;
arc4 roordinated
yielding
%,.l-clim~t.h?-lp?lrirtincl,
romp1 wes
a,~
the
through
to the met.aI ;
rwntnj n 11ncoc~rdinated
srl enwyanate
mf~t.hiuwI
(I. = nntipyrine,
t.he
is not, at twhrd
(fl)
cnnrd i nat e
are
1 i gads
in
because
results
nV~‘r’the C-N-N unit
sib and
(ll),
and 1531.
of the
the IR
144
( rp ) > % I----
[(cp),ZrR2] f Kf2(‘=N=N ___)
(9; R
q
‘u-it
(9 1
Bz, R' = Ph)
(10; R = Me, R' = Ph) (11; R = Bz, R'
CCKEt)
q
(10)
(cp),%r(H)Cl), + Ph>f:=N=N --+
chlorine-bridges
WI the basis of the JR spect.ra [5Fi]
[M((NSiMr,),SiMP,}2]
Thermal dwomposition 60
‘c
and
lV2
t M(:l, ------+ 'LMc.1, 1 (NSiMP3)*Si?k2)
yields
a
[ (~r(lHSiMe,~SiMe:,[N(SiMe3)2])~J, having fused, planar,
rings
and
ana 1ogous the
the hafni
q
2.04-2.09
d~romposit.ion
prcdwt
A);
ring
cent.ral Zr,C, INII camp I PYPF
bridging a
cart~nr~
st.nlcturP
(13)
in
rings adopt a "tub" conformation
four-membrred
and 2.19 k; r(%r-N)
= Mr, Ft , or ('lI,SiFle,) at (J'?
of [H,%r(N(SiYe,),),]
mm Hg
,
the dihdral are
111
[~Hf{N(SiM~3)2J2] WFi.9
inolat,ecl
t(kf(:HSiMp,kSiYe,[N(SiMea)zj(r'y))z] [St;].
(11)
anglw
_ and 123
whirh
three
(r(7r-I:) = '2.15
h+t.w~Pn t.he tin %rNSiC
.
(R = Me, as
~v~mprod,
the
[n
the
I+,
CRSF
of
t-he
or ('H,SiPlea),
pridine
adduct,
145
H NR; 1 \ NR’ ‘C --Z/I I SiMe, R’N I I ‘h--C
Me,Si
I
\
R;N
H
(13; R' = SiMe,) 1,2-his(dimethy~17h"s~hi no
of
RPact i on
[(MC~1,SiMe2NSiYe,[?j(S~Me3)*]]~]
(M
=
%r
or
) et hane
at. room
Hf)
temperature
~K,?1(Y(SiM~,)2J2] (M = 7r or Ilf; N = Me, Et., or W2SiMe3) the his(metaIlaryrle) an octahdral 'L. 3 1 6
=
monn,sidP
rarbon
or with
at 60 'C affords
xirconilnn comples
has
tris(chplnte) strurtllrp of' jdea1i~Ffd c-Z s:mp-t.ry (14) {r(Zr-C) =
T(Y.r-N)
,A ;
TOP
[M?~~SiMe3)z(dmp)].
with
(ctmpe,
2.0xX
i’\;
i-(3-P)
=
20 'c)
(20 atm,
in
2.X52 pntane
kmpund
k).
yielding
(14) rea&.s with compnund
(15);
the
proposed ntrncture of' (15) is based on it1IWR and 13("NMR spectra 1571.
ii”’
CH2 Me2
P 'd, P;;r<
*A
\
,SiMe2 I
I
Me2
PI,
,NSiMe3
p;
NSiMe3 Me2
:
1 ;r< _
NSiMe3 \ ,SiMe2
Me2 0,
1’
CH2 N
SiMe2 / ,NSiMe3
C
SiMe2
!H,
(15)
(14)
RPartinn {H =
Me
r:omplPWS
or as
II-1 NOW and
of
Vh)
the
with
phosphorus F#'l, (M z
~olnurl~ss,
3lP{lt1)
air-
containing %r
and
NVIK spctra
or
Hf)
moisturcof
these
disilylmjde
LiN(Si.Me2(7H,PR, )2
yi.elds l~l,(N(SiM~,~H*~*)*]~] sensit,ive orystalI.inp solids. compundn
are
consistent
with
146 stn1ctruY2
has
which
(16),
been
-stab1
ishpd
Y-rav
hy
t’or
14i t’f’rart
i on
arp
hldentatr,
Cl
(16;
[ZrC:lZ(N(SiM~*(:H2~e,),},]. wi t,h t,he of
t,hP
two
The
\uv:oordinatcu;l
equatorial
approsimatcr(Zr--Cl)
q
The
symmet,ry
2.460
:\;
N(SiM+(‘H,PRR,),
bulky
SiMp,(‘H,PR,
plane.
C2
R’ = SiMe,cH,PR,)
and
Cl-k’1
grarips
resulting
is
HfC14,
yielding
and
can
be
the
[Hf(BH4)4]
by
to
amide t.he
reaction
[Hf(BfI,),{N(SjM~Ft,(‘H,M”le,),)] dinuclear
trihydride
rcith
[ZrCL2(0Ye3)(RHPz3)]
[ZrCl,(CC’Me,)
(HR( 3,5-Me,&,),]
correspond& of on
the
more
stet-inally
rigjd
at
5
ng
or
i.n
scale
hindered
twist
t.hp
of
hasps
up
heen
(A$
z
(Wt.a
1~10 .C.
The
the
synthesis
for
{lIR(3,.i-Me2Pz),)l preferred
prepred
[60,61].
)]
nf the
e
C~0l~)
the
PZ)
and
of’
the
T<;it,h
one
JZ = 1%~)~ vhi 1~ the is
stahl
of
r-nmpl ~YCXT are
st.creochernic~al
ly
mcvhani sm i s
J sPrvl?s or
IV)
r~lar:i-ion
rearrangement
(R
been
gives
nr
) ( WPz,
2 1r.J mol-1
Ul,Ph,
IYi’ f
romplexes
[ %rCl 2 ( WMr,
[%rc‘1,_n(OC~l~,)n(lSR(3,.5-MezPz)3)
also
Me,
Wlea)
hy
[Zr(CX7M~~)R2(HR(3,5-MFf*P~)3)]
have
=
PVYSS
Treat,rnPnt
Ru,
tri-tert-hut.oside
deri\-ativps
of
zirc:nium(
CHM+ ,
of
has
2.1196,
1591. of
1ZrCI,(~~3)(Kn(0,5-Me,Pz)3)
for
prespnce
nr
prepared
56 f
[%rC12(oCMe3) tx
[60].
material
H,
The
=
15Hl.
I,i [f&j.
[~%rc:13{1~3(3,fj-M~zC’z)3)]
t,oluene.
NMR time
t.emPeraturPs
trigonal
stat-t.i
Ko(?le,
=
st r-la-trlr‘p
[~lf(l~H,),~N(Si~p,(‘H,~le,),)
complcvzes
have
1
[I.rCl,(RBPz,)]
equivalent fluxional
(R
t,~ sides
LI~fc~I,(N(Si~lP~l‘H*t’Ple~~,~,I~fCl~
excess
tert-hutoxide
opyx~i
F(Zr-C) ‘1
[ {Hf[N(SiMcsz(‘H2PMF?,),]],(H)3(BH,J,]
Poly(p~~vrazcrlyl)borate t,ype
in
complex
I,ewis
%.iW,
= 119.1(l)
innntps
comptps
an
on
octahc=draI =
N&-N
monomeric with
lc~abct-l
distort.&
= 135.42(A),
“mono”
converted
heing
(T(7r--P)
chiTa
[ Ht’C‘l z (K( Si Fle2(‘t12Wk2 ) 2 } 2 J di spmpnrt
which
ligancts
as
a Useful
derivat
alkyl [Sl].
]
iv+=s
Di (n
=
2
or
and 3)
147 The or
sryl
H-qui no1 i nolat.o-romp1
) and
pr~pard
h;r,
appropri
ate
[(cp)~7,Zr(8-O-quin) mixing
are
S,CWW
121%J .
analngol~c or
S,(loK)
to
[ (cp)2Zr( 8-O-yin)
] [S2COR]
aquenlls
sodi urn
o+Il kyl uanl hate and
.=xes
solutions
(77;
HI,)
in
compolInds
t.hp
ment innpd
the
=
of
Me,
in
Sect
inn
1 : 1 PI ect.ro1ytt.e~
HL;
R = H,
alkyd
have
heen
and or in
the
ptfissi.um ni trobnzene, (V
q
2.1.2.
triethylamine
H
CHMe2)
q
[(cp)7Zr(dikJ]Y
reacts
of
or
[19,62] arp
1 ,?I-dik~t,onato-drrivativ~s
presence
(17;
Et,,
(RR’
1
[ (cp)2Zr(8-0-quin)]ll
hr,.~dialkyldithioc~sr~tt Thwe
I)ichIc,rnt,iR(irIIJ~rIYl)ZirCnni1lm(TV) hasps
(R
] [S,CNRR'
rd th yielding
C6H4R
2-Me,
3-Me,
4-Me)
salicg~~ldimine complexes
Schiff of
the
type
148
H -N t
‘N
/*
H’-3
R
Ph
R = Ph,
r--,
C,H,O)
(18;
M,;
(20;
H,L' ; R = H, Me)
(19;
HI.,;
R = Ph,
r----l
C.&O)
(21; H,L')
OH X H
(22;
H,L'; X = H, S-Cl, Fi-Br,5-NO,,
3-O&,
5-O%,
3,5-Cl,,
5,6-benzo)
149
and
I
151
R2
(33)
The reaction so
red-brown of
111 NhR syxtrtra
quivalent,
phosphi
(:sHs
to
prnt nns
with
[ (c~)~WI~]
I ut i nn .
the
[{(~p)~M(F?le~)}~]
prot.ons
two
do-hr
31P
t.wo
and
a
nllclei
st.nxtltre
i dgcul
equivalents
t.hess
of
%r or
(M =
of
complexes triplet.
.
‘I’he
(24),
with
Hf)
compl~~cs,
I.iFTle2,
exhihi
are
t. a
t311e to
virt.ual
spect.ra
are
ohtained diamagnetic
sharp
singlet,
cn11p1 ing consi
significant,
‘Z,r.
by
due
of
t.he
stent
* .%I-
in to
PMe,
wit,h
a
interact,ion.
Me2 CPI,,
ip\
,,\ CP
cP iMiW
/“‘\cp P
(24) IZearti
nns
of
resell
t, in
give
[(I-~)$LY~]
the
[
cl savage
Photo
(S
[ ( (?leq)z%rH(ti-H)
)21
ic
I ene
t.n
paramagnrtir of of
~(II~-c,D~),~~L,I,
in of
another
give ]
[73]
zi rconilrm( [(c’p)2%rcl*l
i.4
G,
r;hirh
i ndicat.Ps
halogen-containing
and
ouidati
on
of
species t.he
metal
t.a
75 of
.C and
It,
sol ntions
a
benzene
formation
i ndi.cate
r:oritplPX ~irccvri
of
of
the
rlrn( T1 I )-hydride
dark
of
purple
presence
which
,
slurry
of
a
with
rearts
perhaps
species,
. Tl t)-hydride are
is
at
evolution these
7:ir,conium(TIt)-h~r~ri~jC3
(PhCrCPh)
i t.t,ing
heat,ing
r~s~~lt.s
[ (WI-p)z%r(tl)
spl
bonds
i71].
prnlong~
13i ph~~nylac-et,;v
solrlt,itrns
metal-phosphorus
EPR spectra
sn l.l~t.ions. pai-amagnet
the
= halogen) or
Lysis
wi t,h
{ (cp),M( Wle, ) )2 1 oompl wes of
reduced
not, observed t,hat.
t,he
complexes wi t.h when
are
also
produced
magnesium. t,he
experiment
zi rnoni um( T‘II ) -h:-dri
rl~
when
A
‘H
i.s
repe2t&
is
thf
hyperfine
prociured
with by
152 abstraction
hydrogen
from
zirconium(JTI)-hydride reduced by magnesium
a
complexes
cyclopentadienyl
were
observed
by RPR when
photo&is
studies
Led to RPR characterization
the
a
sol.utions
zircnnium(TTT)
in
cyrlohesane
species, The
hydride.
[ (cp)zZr(PEt,)R]
contain
[(cp)zZrRz] complexes are phntolyed
2.3
was
of
(R = H, Me, cp, or Cl) have
of a number of zirconium(TTT)
and
[(CP)$rc11, that
[(cp),ZrCl,]
in toluane or methyl
[(cp),ZrR,l (R = alkyl or aryf) or {(cp)*Zr(R)Cl]
suggest
Additional
in the presence of alkenes or alkynes [76].
Low-temperature
[(cp),ZrRl,
ring.
including
EPR
adducts
spectra
r&en
the
the presence of PEt, [77].
ZTRCONIuM(f) CWlFWNDS
The layer structure of ZrCl and ZrBr can be intercalated with oxygen and hydrogen atoms yielding interstitial derivatives of the monohalides. Cl or Br) reacts with ZrO, at ca. 980 “C according to equation
ZrX + r1Zr0~ _
and ycan
ZrXOy + riZrOx
take on values up to CA. 0.4.
consisting
of
four-layer
slabs
ZrX (X =
(121, where s
(12)
The pure monohalides have a structure
with
stacking
sequence
X-Zr-Zr-X.
X-ray
studies have shown that in ZrXOUv the oxygen atoms are randomly distributed
in
tetrahedral interstices between the double zirconium layers of an expanded ZrX structure. ZrC,
Reactions analogous to equation
ZrN,
ZrF,,
or
Zr,+,S,
and
attempts
small molecules were unsuccessful Guinier ZrBrHoe5,
X-ray
ZrBrH,
data
ZKlH
also
indicate have
zirconium
tetrahedral
layers;
interstices
photoelectron
the
intercalate
hydrogen
between
the
that
expanded
formation is accompanied by a progressive adjacent
to
with
several
the ZrX
monohalide
hydrides
structures.
Hydride
increase in the distance between the atoms
zirconium
are
presumed
atoms
to
[79].
occupy
X-ray
and
the Crv'
spectra of ZrXHc*a, ZrXH (X = Cl or Br), and ZrH,.,, indicate an
appreciable amount of Zr-H covalency
[80].
Trends in XPES data for zirconium, ZrCl,
(n = l-4), ZrBr, ZrxH,
or Br; x = 0.5 or l), and ZrClOo,, have been reviewed. the zirconium
ZrCl
[78].
powder
and
(12) do not occur between ZICL and
3412 level
oxidation
state
except
displaced
to higher
exhibits
a regular
for ZrCl, and
binding
energy by
(X = CJ
The binding energy of
increase with
increasing
ZrCl,, where
the binding
ca. 1.3 eV.
The break
formal
energies
are
in the trend,
t.ris(%,2’-hiI,vricline)
The [Fl(hipy)3] by
and
rr4uction
contain
a
C’”I 0l~7Fd,
[M(phm)3] of
or
HfVl,
stnirheiomet,ric
Hetwohimet.al1
ir
h?; react inn of
st.ruct.lrre
of
.wnnit.ixx=,
prepared
the
of‘ the
in
a met.a 1-rwt.al
with Iwnd
type
t.hese
of
.(25)
80% yield that.
arp
dark
[82].
[(cp)27i%r~((.~~)z(~p)
compunds
[(cy))2(MF131:O)7rR11(Cc))2(cy))]
ca.
solutions
rc>mptpses
and diamagnetic
one equivalent. in
in
t.hf
These
Ijgand.
Ru; N = COle3 or Me, r+hen M = Fe)
[ (cp) ,%r(‘tX]
nf
ha.x+e ken
ncxxlium amalgam
monomeric,
complesen
q
Hf),
of
compl eses ,
t.ris( 1, lo-phennnthroline)
vit.h
;unolInt
air
CX74est or Me, when ?I
prcwww
(Fl = %r or
%
extremely
and
have ken
]
(X = r-1,
synthesized
li[(~p]M(C0)~]
in thf.
was confirmed
by the
{r(%r-Rut
q
The X-ray
2.910(I)
A;
CP
(25) r(%r-0)
= 1.910(4) The
iI; Zr-6-C
compl exes
[ (cp) W(rCC1611,Ple-4) ((‘0) z ] and relat.i.vel
y inert
= 169.6
-1 [X3].
[(~I),M(CO)~I
in
to I wne
(M at. 55-70
bimet.n I I i.c compwnds
=
Ti
Zr)
or
‘(“ t,n give
the
[ (cp)$l(~-CC,H,Me-4)
rf?,xA.
thermally
with stable
(c~-C~~)W(C~)(Cp) ]
C,H,Me-4 I
1. 2. 3. 3. 5. 6. 7.
x. 0. 10. 11. 12, 13
.
14 . 15. Iti. 17. 1X.
155 19.
Ii.
Khera
1:1
(19H:l)
N .li.
?kta
I-Ckg.
.j.li.
Iiaushj
F1. iihera, 13
f‘hem.,
Sharma,
rN~ta /-Org.
n.
13
23. 21.
iFLSW, Div. Kh.
n.1..
?lntnv Nikitina
29).
1j.I..
nnd
N.K.
Metal-Org.
Jia\lshi k,
.‘$nfh.
Rw~ct.
lnorg’.
Karlshi
Spth.
React.
fnnrg.
Chem. ,
k,
10.59.
N.K.
Kaushi
Iia;Fillshik,
k,
J.
Indian
YIP. and
(1983)
Rogar~hw~,
P.
and ().,A. Mi khai
31 ( 1482)
1429.
fbainina,
%.S.
R7s.s.
Zalkina,
liooro’.
( 1983) 399.
1 n\;a,
Klemenkova,
J.
i
Snc.,
Ru.1Z _ Acad. Sci .
B.V.
Iokshin,
T.D.
, &II I. ,Jr;ld.Sri. LX-Z', RPFIC~..Inorg. ~~Iet.~I-Org.
Inorg.
fhem., 27 ( 1982) (1983)
[ihim., 9
IO.57
1X0-1.
[C’hem.
1487151.
I..M.
Pnmi-Knshits,
Soxi nova,
0.4.
Chwn. 113
?\onatsh. fhpm.,
Xinarheva,
E.V.
and
9!4
Ahstr.,
34 * 35 .
rnorg.
T , %hdannv, and P.1.‘. Petrn\-ski .+i . , 3% (lwx! f)iI..i%rm. 126.5. S , S:*xena , \-.P. Singh, and A.!<. I?ai, .‘?.rnth. c-hem., I:< (1983) 855. S.D.
31 . 32. :i:<.
A?eart.
S,
27. 2x ,
30.
and
.Sr-i .,
Minachwa,
N i kol AI~GX,
26.
Sodhi
Cbrm.
N.K.
(1983)
13. Jihw-a
, G.S.
and
Khera,
I’hc=m.,
60 (lW3) 209. A.[<. Sharma and N .I\. PI. Kh. li.Pl. JIrai nina, M.
.S.r-nth.
( 1983) :1X1 .
22.
2.5,
k,
357.
Sharma,
A.l\. ‘21 9
and
J.
Dikarewa, .StnxV.
V.
1-a.
K~tznetsov,
I,..!?.
Fomenko,
and
M.A.
76.5.
Them., 23 (1982)
>lc~l ‘ni iron-a, II. K. F:f i mov, S. K, Vasi n, and V. .A. Fledvedev, Russ. J. I-YI.I:~, ('hem., 57 (19,83) 991. S. Singh, M. I+di, and JI. V:erma, .I. F’lrlorine Chem., 20 (1982) 107.. (1. ‘I’hwalt, and k’. laswr, Z. rVatruTorsrh., 7’eil R, 38 (1983) 1501. 4 .V. Dudi n, V. P. Baharca, and V.Va JZosolovski i , RIJSS. J. Tnorg. Chem. , 2x ( 1w:4j 950. I[. T
(‘hem. ,
rnorg.
36. 37.
R.K.
hgar-wal
I?.K.
,Agarwal
98 .
Yu. \-;I.
Thrrmwh
im. Khar
(1982)
39 .
P.E.
Riley,
10.
t4.F:.
Silver,
41.
M.A.
Si Iver,
42.
S . Jillmar,
33. ,l4.
W.1,.
Stctffen,
4.H.
nr~~der,
Thermochim. Arta, 63 (1983)
PI. Srivastava, l3.S. Ada, 61 (1983) 235. i t.onov , M. M, Wkhi t., K.
Ah{]-l%wi,
and
ICisenst.ein,
and
R.C.
FRY,
and
S.F.
A.R.
113.
Srivastava,
J+Lr=vski
i,
RIISS. J. Tnorg.
1i.N. Raymond, and R.C. Fay,
rnn0r.g.
(Xem.,
Inorg.
22
(1983)
3940.
Chem., 22 (1983) 759.
Or:g,wwm~tailirs, 2 (1983) 44 lialshik, Russ. J. Tnorg. Chem.,
N.K.
and
Stxlhi,
G.S.
and
Tyagi,
1109.
0.
(l!w:{)
1582.
,
(1983)
rhrm., 28
2K
27
;md S.C. &~nto~i,
196.
H.Ji. R,.C:.
and
Chlln, Fay,
D.F.
K.C.
Fay,
Lewis,
Tnorg.
and
A.A.
17
Chem.,
Sayl.er,
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