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or bases
107
JoumalofMolecularShucture,47(1978)107-127 OElsevierScientific Publishing Company,Amsterdam-MhintedmTheNetherlands
SPECTROSCOPIC ACIDS
STUDIES
AND/OR
OF RETAL
CHELATE
COKPLEXES
AS LEWIS
BASES
Yordanov, Institute of Organic
N.D.
1113
Sofia,
chelates
of
important
chemical
these
react ion have
of the donor
is very
different
and acceptor
Sciences,
properties
for the understanding
and biochemical
reactions,
is one way to have more
mechanism.
In view of this
used
study
to
and donor or acceptor
obtained
report
with
of some planar
metal
their
deep
role in
insight
spectral
between
metal
on the
methods chelates
fl - 31 . .
the attention
different
of metal
The investigation
different
the interaction
molecules
In the present
action
of
Academy
properties
been
results
Bulgarian
Bulgaria
study
The
Chemistry,
spectral
chelate
is concerned
methods
complexes
to the
on the
with
inter-
Lewis
bases
and acids. The metal in
several
chelate
different
complexes
ways /Fig-l/:
with amines;
exchange
coordination
of the bases
Jf the complexes. complexes
axial
given metal
coordination
coordinated
also
oxidation-reduction
along
condenzation
takes
cqse
be considered
groups
complex
place;
bases
in the ligandsj
of the interaction
and weak
Lewis bases
bases
position,
between
for all
in details,
the strong
in the equatorial reaction
Lewis
of the ligands
is common
that as a result
chelate
with
the 2 axis or in the plane YCJ
the latter
it will
It is established, between
interact
of the functional
Since
studied,
can
only
can be
and in some
the reactants
occur.
cases
+
R’NH2
\
i- R”NH
/
Lb de B
B
B
Fig.
1
Scheme and
The
energetic
configuration as
of
reaction
Lewis
the
in Fig.2.
of
iigand
the complex
electronic
structure
plane physical
z
metal
complexes
field
It Ss seen
will move
coordination
planar
metal
chelate
complexes
bases
diagrame of
between
can
be
from
in
represented
this
to more
different
figure
high
along
can be registrated
by
methods.
from
Some
data
that
symmetry
will be changed,
of the bases
generally
and
Hence,
the =-axis, different the
axial
coordination
therefore,
the
process
as well
spectral
electronid
its
of
as in ths
and other
spectra
of NfL2
Fig.2
Energetic
dia&ram
configuratian
and
from
this
transitions energstic
strongest
shifted *
diagram case
orbital
the
2
) are
fer some and
case bands
of
results 2 below)
varied,
on
axial
shown
in Table
energies
of
1, and
all with
coordination
the
the
dr2,
dxr,
with
the
method
weak
can
b8omS8
studies,
the
in different
field
correspondence
interacts
these
masking
the
in
*Spectrophotometric every
jigand
is on
(Fig.3)
complexes
it
can
be
electronic the
above
. of
influence
metal
that
Table,
are
In the
dr2
1 or
NiL2. 3 x (x=
seen
of
for
s - d
equilibrium
evaluated
by
use
of dyr
bases,
metal
not Of
bands.
used
be
different
be
of
2
with
intensive Ray
the
orbitals,
corresponding
constants of
the
or
p
success
in
charge-trans-
for
process
spectral
The
this
reason
(se8 methods
eq.1
3.10 TABL_E
spectra
Electronic
1
of Ni(I1)
bisidithiophdsphate.
in different
E1
Solvent
solvents
(in
E2
E3
complexes
cm -9
Ref.
benzene
74
SDII
19 200
26 000
192
p yridine
0
550
9 000
14 900
192
21 834 21 600
2
12 820
d-picoline
13
0 -picoline $-picoline 1.
3
8 550
9 810
14 930
2
8
9 010
14 930
2
550
This paper
2. H.E. Franics,
G.L. Tincher,
G.Pl. Woltermann 3, R,L, Carlin,
orbitals the
850
of the bases,
corresponding
molecules electron
wil1 be more
hiqh
IO,
Losee - Inorg.
2620
Chem.,
J, R.
orbitals
in axial
the electron
Wasson,
(1971) 2, 2084 (1970)
and d,, and dyz orbitals
e or x
coordinated donors,
Chem.,
- Inorg,
O.B.
W.F. Wagner,
interact
from the bases.
position transfer
than that through
Since
of the complex through
donor
the acceptor's
with the
are fiv bonds
5
-dative
bonds, Now we vi13
consider
our attention
namely,
uhen two electrons
(Ni(I1)
and Cu( II) complexes),
this
orbital
lied orbitals, Cu(II)
( Ca(I1)
are located and
complekes),
in all studied
), they are filled,
when
Since here
to two typical
cases,
on the d,2 orbital one
electron
occupies
the dXz and dyz are low
complexes
(
Co{
II), Ni(II),
111
6.2
Metal complex
Fig.3
Donor molecule
Axial
interaction
between
and the appropriate .
In Ni(I1)
planar
orbitals
chelate
complexes
when one or two base molecules
the 5 axis,
the ground
state OP NiL28,
(b2g)2(a,,)'(b,g)'~
and the complex
can be registrated
by use of magnetic
tion
[2, 6, 73 , that
in Cu(II)
of the base molecule
electron
transfer
Prom the
state
is
are diamagnetic.
are coordinated
along 4 ( x = 1 or 2) is (e,)
becomes
paramagnetis,
spectral
chelates
( or molecules filled
dyr orbitals
the ground
methods
by the use of magnetic
It was established, methods
dr2, dxZ,
from the base molecule
and the complexes
(eg)4(b2g)2(a,g)2(b,g)o However,
the metal
dZ2 orbital
[4,53 .
spectral
the axial
) reeults
which
coordina-
particular
to the dX:2_
Y2
112 arbital,
on which
the unpaired
case the complex rhombic
becomes
distortion
the electronic
expended
in this
structure
corresponding
changes
unpaired
in Table
Since complexes
nuclei
the unpaired
magnitudes pK
in the electronic the decreasing
u,with Some
of the
of the
the magnetic data about
for some copper
electron
in Co(I1)
on the d,2 orbital,
of bases
is observed
with
nuclei
these
complexes
2,
is located
coordination
in
EPR parameters*,
interaction
(shf)
ligands.
in the shf interaction
are given
shf interaction
planar
as a result
with
chelate of axial
their magnetic
[9 - 131 . It was established
of this shf interaction
is in some
also that the
correlation
with
values.
*Since nated
chelate
changes
of their
is for example
in the plane
and some
are conected
changes
of the superhyperfine
from the equatorial
their
of these
electron,lies
changes
complex
In this
x,
is obtained--The
in the magnitudes
of the complex
magnitudes
is located,
in the plane
plane
of the
The mosr. clear evidence structure
electron
the exchange
between
the coordinated
state of the metal
complex
is very fast (see below),
results processes
have
been obtained
of coordination
the complex molecules
in solution
in the solid
by using
the analogy
of base molecules and selfassociation
state,
and noncoordi-
between
along
the
the taxis
between
and the observed
these of
compfex
equality
in the
shape and parameters of the EPR spectra in both cases i72 . Here we wish to note that some autors have no success in simulating the
theoretical
until
assuming
coordinated
EPR spectra rhombic
complexes
coinciding
distortion 681
.
with
the experimental,
in the plane
x~ of the
113
TAELE2 The
influence
Cu(ox)2, of
the
of
Cu(tox)2, s.h.F.
Base*
Complex
cdox)2
axial
coordination
and
Cu(dmg)2
interaction
A,,
with
+O.SG
of
base
complexes the
on
2
chelate
ligands
(G)
A,
13.5
10.5
11.5
0.8
PY
11.8
9.2
10.1
0.7
qu
11.3
8.8
10.1
0.6
.-qu
12.4
9.6
10.5
0.7
IMFA
11.4
8.8
9.7
0.7
Tht
13.3
10.3
0.8
11.3 TO.9
16.2
13.0
14.1
0.9
PY
15.7
12.5
13.5
0.8
qu
15.7
12.6
13.5
cl.8
DRFA
15.3
11.9
13.0
0.8
PY H2°
DMFA
along
magnitudes
Aiso(G I
AL-+0,5G
13.5
Diox
Cu(dmg)2
the
equatorial
Iiox
cu(tox)
rroleculss
19.3
15.9
17.0
0.9
18.6
15.3
16.4
0.9
18.5
15.6
16.6
0.9
*
PY - pyridine;
-
dimethylformamide;
qu
- quinoline; THt
-
i-qu
Thiophane;
-
iso-quinoline;
Diox
-
dioxane.
114 In most metal
cases
complexes
the axial
coordination
is equilibrium
process
of bases
to the
Cl - 37 :
% MeLx + B a-
meL,.B
(1)
Ir;! PieL .,B and the equilibrium use of different procedire
+
spectral
is given
the
type
of
IrieLx.B2
k, and 5 can be estimated by -2 methods ( for electronic spectra the
in fi41 9 or for EPR
lc,77g2,
( metal
given pK
of _, k obtained
complex
values
of
by studing
and different the
bases
was
bases found
TABLE -pk
values
(at 25OC)
of
some Lewis
or
Base
pK*
Comparing
the between
no good correlation .
The
with the
pK data for some
bases
and equilibrium
CuL2 + B 7
dithiocarbamate)
in
constants
CuL2.B CHC13
Cu( acac)2
(
cl71
.
Cu(
dt c) 2
5-11 + 5.34
2.95
o-17
i-quinoline
5.36 + 5.42
2-30
0.18
quinoline
3.97 + 4.96
0.48
0.029 0.06
thiophate
-5.10
+ -4.52
O-28
dioxane
-4.3
+ -2-92
O-27
organic
from D-D,
bases
Perrin
in aqueous
"Dissociation
solution”,
London,
constants
k -1
L =
pyridine
*Data
a
3
for the reaction
acetylacetonate
separetely),
the interaction
[16,17]
- in
of k, depends
and ligand
of the bases.
as well as on the properties magnitudes
and NMR spectra
and the magnitude
complexes
the
(2)
constants
6'151 )- In all cases on
B 4
of
Butterworths,
1965.
115 Lewis
bases
copper
and the corresponding complexes
The acceptor important
are shown on Table properties
for the values
112' In copper chromophores
chelate in which
> Cu(02N2)
The acceptor
Lewis
7 Cu(N4)
bonds
character
increases,
on the metal
of the
p
in the
interac[2]
:
7 Cu(S4)
7 Cu(Se4)
decrease
in this order.
in this order
and therefore,
order
k and -1 of the
has been established
>Cu(N2S2)
that
are
constants
of k, decrease
of the complexes
Howe#:er, it is well known, the covalent
complexes
the following
base
for two
3.
of the equilibrium
the values
properties
of k, obtained
of the metal
complexes
tion with one and same Cu(O4)
values
of chromophores
-metal-equatorial the remaining
ligand
positive
charge
ion decrease.
The properties the magnitudes
of the solvents
of the equilibrium
of the specific
solvatation
are also
constants
of the base,
important
for
k, and =2' k because
and that of the
complex[l6,1]. Since the forward
the equilibrium (5)
it is possible NMR.
The
changes
and the backward to obtain
values
of $
11, is the
(&)
rate
and/or
k+, could
ratio
between
constants
of (I),
by the use of EPR
its magnitude
in the line width
coordination.
constant
be estimated
in the corresponding
and
from the
spectra
due to
For the reaction kf Cu(dtc)2
+ B _T
Cu(dtc)2.B
(3)
-b when B = pyridine k& = 0.37x10
9 set -'
Valuable structure
&
= 2x10
9
set -1 , and when I3 = piperidine
-
c78 3 .
information
of the bases
about
induced
the changes
by their
in the electronic
coordination
along
the
116 f, axis of the metal netic
in PMR
shifts
to
223 . This bonds
the
found
to decrease atom
and undependent the ring
the paramagnetic
-system
X7
of the heteroatom.
of the paramsgnetic in axial tional
position
to their
chelate
is coneected
spectral
properties.
ligands interest several
since orders
complexes
than
with monodentate
of the base
distortion
and expansion
possibility
for opening
of these
of the complex of the chelate
on Fig.4.
the equatorial
in the following
of the bases propor-
of the metal
changes
in their
of menodentate is of special complexes
constants
It was suggested
as a first
ted. The scheme
explained
complexes
of this process
of the base
Formaly,
electron
are in general
the corresponding
way and the coordination is shown
the
that the magnitudes
of coordination
constants
(or bases)
are equal
and therefcire, in their
ligands.
that the mechanism
6, 261, nation
higher
and aroma-
G 23 - 251,
in the plane XJ
of the chelate
the stability
-
_
structure,
=
r-
with
with considerable
The problem
in the plane
on the
of all protons
complexes,
of Lewis bases
and electronic
619
in the molecule
c24,25]
of the
metal
due to the coordination
to the metal
geometry
the
like aniline
It is established,
pK values
complexes
shifts
piperidine,
increasing to
is superconjugated
shifts,
Coordination
with
bases
position
The paramag-
like pyridine,
delocalization
In conjugated
of their
by MR.
coordinated
is due of the electron
tic phosphines
pair
of bases
functional
of the bases.
since
are abtained
spectra
etc, were
quinoline, distance
complexes
includes
of the
recentlyr2, axial
step providing
coordi-
rhombic
in the plane x~_. The ring
is increased
in the plane x~
coordination
way /Fiq,S/:
are in
in this
is facilita-
of the base
If we consider
could be the
117
Fig.4
FSechanism to the
of
equatorial
metal
chelate
(A)
coordination
%a- I-
= l/2
x2
+
molecule
d,2_Y2)
1
XYZ
piz-
base
ICI
( dz2_
-
xy2
the
complex
(a, 2
of
dz2_ x2
2
%2_ Y2 dz2_
Y2
dXz dXY dXZ
Fig.5.a)
Transformation
metal b)
chelate
Changes
upper
species axial
base
after (A
in
will originate molecule
The
xyz
coordinate
into
XYZ
(see
of
the
metal
signs
system
the
of
the
text).
orbitals
dck
to the
transformation
position
A
the
complex
in the
obtained
x/2
of
new
xy~ , but only
coordination Fig.5),
of
rotation
position
B on Fig.5.
in the
plane
coordinate
system
XYZ
axes
are
rotated
base
around
is situated
the
the
molecuke
the
in
x or 1
axis
In this
position
XY* -
and
two
of
have
the
same
with
z/2.
the
centrum
in the
donor
as
118 the
~c01;i.sProm
back
to
the
nated
on
state
C will
the
state
this
Powewer, go
chelate
the
is
state Z
dZ*_
the
be
r* =
the
ortsitals
the
dx2
_
d,2_
the
base
molecules
position, plane
as
are well
Evidence of
x~
splitting
due
Typical
example
stable since
arbitrary The
d,*_
are
Y2
to
having
ortlital
y*
fully
that
for
of
to
planes
the
on
case
the
are
rotation
shown
the of
plane
equivalent
The
orbitals
applied
(4)
their
another).
met21
)
Fig.5',
when
two
complex
bidentate
will
traasbase
in
place. coordination the
case
EPR
of
magnetic
coordination
in the
plane
x~
in the!_r EPR
effective
overlapping
the metal.
reaction
-
+
one
interaction
splitting
and
x*
cooroination
give
this
the
coordi-
the
spectra
the
nuclei
are
of
in the
bases
in which
shf
unpaired
electron,
from
bases
the
copper(I1)
chelate
lying
occurs, complexes
.
The bases
for
will
is possible
complex.
in the
takes
the
axis.
atoms
2nd
cboosen
fact
be
equatorial
the
with
plane,
307
when
complexes
to
in this
c 26 -
as
XY -
procedure
the
the
coordinated
for
the
of could
position
in cis-
plane
(normal
method
oonor
been
d,2
2nd
transformation
Analogous
chelate olane
(1/2P(d,*_
excluding
perpendicular
complex
on
2s:
x2
y2 orbital
the
starting
represented
and
provide
the
therefore
the
has
Xyz
1.
the
The upper
of
d~2_
mutually
one-of to
the
situate0
end
move
System
geometry
can
r2
will
realized.
be
are
unstable,
A, or
axis
coordination
in mind
ligands
are
of of
molecule
the
complexes
spectra
have
between
Therefore,
performed
the
and
21
conditions , and
molecules) the
provided
the orbitals
some
131,
(or
of
existence
the
the of
existence
shf of
of the base molecule for
electron
oxidation-reduction transfer
is possible
119
depending
on the reagents
of piperidine plex
shows
have
been
with
copper
with
copper
equatorial
and other
-thiooxines, chelste
comreaction
interacts
-dithiocartamates,
lignnds,
the redox
-di-
reaction
place 1 2, 263.
take
Wetal
chelate
interact
complexes
with
they
will
could
be@
other
atoms of the ligand
donor
metal
atoms
chelates
acceptor
molecules
the spectra shows
during
obtained
Gr, NO3r ClG4)
molecules
magnitude
the
of mixed-figand
to the changes the
gives
in the
and for
complexes by the
complexes.
of the type bis( X = Cl,
, C(kG2),
isotropic
the presence nuclei
g-values of
in
fig.6
copper
6353
for the suggested
of
and
chsnges
such like CuX2
and 7Q98'8r
between
formation
complexes
and SbGr3
hf interaction,
the evidence
the
between
and acceptord
conplex,
complex&s,
chelate
followed
c32 - 343, SnCl4
of
results
interaction
centers
system,
and the resulting
due to one 3%37Cl,
splitting
metal
donor
The inters&ion
or charge-transfer
conviniently
complexes
In addition
spectra
is
ion.
and therefore,
of the
j't -eronatic
metal
between
EPR spectra
dithiocarbamate
etc.
the
of the starting
several
CuXdtc
-
or its
and acceptor
The interaction
The
molscules.
from the chronophore
mixed-ligand
modificated,
act also as donors
acceptor
complexes
Co( II) planar
the
interaction
but redox
of the base,
when the same base
However,
bis-oxines,
thiophosphates,
the
bis-hexsfluoroacetylacetonzte
coordination
not observed.
Far example
propertiEs,
the
kO26363, end shf
in the EPR
mixed-ligand
structure*,
*In the solid r3.73 *
state
these mixed-ligand
complexes
dimerized
120
I
Fig.6
I
EPR
I
spectra
interaction Cu(N03)2
I
of mixed-ligand of Cu(dtc)2
cux* the presence
was established
The EPR spectra ligands from
of the
are shown
between
obtained
CuC12
(b), CuBr2
complexes
of the solvent's
complexes
containing
35.37 Cl and 7g*81 Fir nuclei
and
contain-
and one dithiocarbamate
depending
where
the
(c),
bis-dithiocarbamates
copper(I1)
(or bromine)
in Fig.7
during
(e>
Ni(I1)
of mixed-ligand
ing one or two chlorine ligand
(a) with:
(d), and CU(C~O~)~
In the reaction
complexes
well could
properties
c383
one and two halogen
resolved
shf splitting
be easily
recognized.
121 NI
NI (dt+
(dtc12 + CuX2 (X=CI, Er)
.
.
Cuxdtc
[CuX,dtc-j-
Fig.7
a -X=Cl
c-Y-N4
a-X=Cl
b-X=Br
d - Y = ClO,
b-X=Br
EPR
spectra
during (b), right
the
of
mixed- ligand
interaction
CU(NO~)~ -
+ CU*+-----
( Y = q,
(c),
in acetone
of
CU(C~O~)~ or
[cu WtG] + c-Y=NCL, d - Y = CIO,
copper(I1) Ni(dtc)2 (d),
equivolume
ZY-
C104)
complexes
with:
CuC12
left
column
mixture
of
obtained (a),
CuBr2
in DMFA EtOH
and
and CHC13
122
The interaction proceeds
as a redox
Special Pt(II),
of these
is shown
is formation
there
The
433.
a charge-transfer
These
have
teen
bases,
x-aromatic
oxines,
X-acceptors
etc.
which
spectra
conclusions also
by
etc.
precipitates
r39 -
of the precipitate band,
system
attributed
of the ligands
for the formation X-ray
in
as tetra-
tetracyanoquinodimethane,
;z‘ -d onor
conFirmed
nickel(II),
containing
of a new absorption
from the
;;C-acceptor.
complex
schiff
with
electronic
shown the presence
acids
copper(
with ligands
complexes
Lewis
.
of a new compound
reflectance
with
toward
trinitrobenzene,
cyanoethylene,
the
c353
complexes
etc.
complexes
such like salicylaldehydes,
the reaction
have
reaction
interest
Pd(I1)
system
of some
analysis
to to
of CT
644
-
497
9).
(Fig,
It was shown coordinate
that Co(I1)
Lewis bases
es are effective
oxygen
coordinated
along
lished
also
along
properties,
ligandsl50,
511
effective
oxygen
chelate
the f axis,
carriers
complexes
However,
and the oxygen
these
of the 02 binding
can complex-
molecule
the L axis of the complex.
that the reversibility
on theredox
planar
is
It was estabis dependent
e.g. of the shape of the equatorial
, and it is assumed carriers
that at the moment
are the Co(I1)
bis-schiff
the most
base
complex-
es &!52,533 . The interaction Lewis
acids
regulation solvent
and/or of their
bases
plays
activity.
reagents,
interaction
Thus,
chelate
an important In most
on the rate of the chemical
to the specific the
of the metal
between
cases
complexes
role for the the influence
reactions
of the
can fie attributed
the solvent
the rate of the reaction
with
molecules
between
copper
and
123
Charge-transfer
band
energies(cm-')+
+AS Bolley.R L P Wllllams.J Dwrlght-J Chem Sot. 2579 (1965) Fig.8
Schematic
representation
complexes
and
chelate
complexes
more
than
weak
Lewis
during
the
peroxides fact
be
coordination equatorial 1 igands
and
c!i4]
reaction are
can
chloranil
some
3 - 4 orders bases
are
.(The
remains
explained
plane
the
organic
increased.
the
hydroperoxydes OF
that
as
complex
donor
the
the this
a result
metal
organic
of ion hydro-
experimental of
the
extended
properties
between
(1:2)
quaotitis
of
becomes
interaction
Me(ox)2
increases
small
state
acceptors,
the
between
trinitrobenzene
unchanged.)Since
therefore, The
and
oxidation
assuming
and
complexes
presence
strong
base,
CT
(1:l)
in the
relatively
of
of
halogen
axial in the
of
the contain-
124 ing hydrocarbons sence
or’
1553
.
are
weak
weak
Lewis
bases
It is well
known,
Lewis
structure
acids the
OF
the
ced,
and copper
react ion
could
and
takes
mixeo-ligand
be
do
not
induce
but
if
place
in
any
weak
and
complexes
The application
explained
OF different
acceptor
metal
complexes
wide
of the fine mechanism reactions. be extended
bases
spectral
of the donor-and/or discovers
in the are
introdu-
stage
of the
formed.
investigation chelate
pre-
mannier
same
changes
Lewis
the
hydrocarbons
in the initial
are
in
the
that halogen-containing
complexes,
reaction
complexes
bis-chelate
of difFerent
methods
properties
sources
chemical
In view of this the studies
on the of the
for understanding
and biochemical
in this
direction
will
in future.
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JoumalofMolecularShucture,47(1978)107-127 OElsevierScientific Publishing Company,Amsterdam-MhintedmTheNetherlands
SPECTROSCOPIC ACIDS
STUDIES
AND/OR
OF RETAL
CHELATE
COKPLEXES
AS LEWIS
BASES
Yordanov, Institute of Organic
N.D.
1113
Sofia,
chelates
of
important
chemical
these
react ion have
of the donor
is very
different
and acceptor
Sciences,
properties
for the understanding
and biochemical
reactions,
is one way to have more
mechanism.
In view of this
used
study
to
and donor or acceptor
obtained
report
with
of some planar
metal
their
deep
role in
insight
spectral
between
metal
on the
methods chelates
fl - 31 . .
the attention
different
of metal
The investigation
different
the interaction
molecules
In the present
action
of
Academy
properties
been
results
Bulgarian
Bulgaria
study
The
Chemistry,
spectral
chelate
is concerned
methods
complexes
to the
on the
with
inter-
Lewis
bases
and acids. The metal in
several
chelate
different
complexes
ways /Fig-l/:
with amines;
exchange
coordination
of the bases
Jf the complexes. complexes
axial
given metal
coordination
coordinated
also
oxidation-reduction
along
condenzation
takes
cqse
be considered
groups
complex
place;
bases
in the ligandsj
of the interaction
and weak
Lewis bases
bases
position,
between
for all
in details,
the strong
in the equatorial reaction
Lewis
of the ligands
is common
that as a result
chelate
with
the 2 axis or in the plane YCJ
the latter
it will
It is established, between
interact
of the functional
Since
studied,
can
only
can be
and in some
the reactants
occur.
cases
+
R’NH2
\
i- R”NH
/
Lb de B
B
B
Fig.
1
Scheme and
The
energetic
configuration as
of
reaction
Lewis
the
in Fig.2.
of
iigand
the complex
electronic
structure
plane physical
z
metal
complexes
field
It Ss seen
will move
coordination
planar
metal
chelate
complexes
bases
diagrame of
between
can
be
from
in
represented
this
to more
different
figure
high
along
can be registrated
by
methods.
from
Some
data
that
symmetry
will be changed,
of the bases
generally
and
Hence,
the =-axis, different the
axial
coordination
therefore,
the
process
as well
spectral
electronid
its
of
as in ths
and other
spectra
of NfL2
Fig.2
Energetic
dia&ram
configuratian
and
from
this
transitions energstic
strongest
shifted *
diagram case
orbital
the
2
) are
fer some and
case bands
of
results 2 below)
varied,
on
axial
shown
in Table
energies
of
1, and
all with
coordination
the
the
dr2,
dxr,
with
the
method
weak
can
b8omS8
studies,
the
in different
field
correspondence
interacts
these
masking
the
in
*Spectrophotometric every
jigand
is on
(Fig.3)
complexes
it
can
be
electronic the
above
. of
influence
metal
that
Table,
are
In the
dr2
1 or
NiL2. 3 x (x=
seen
of
for
s - d
equilibrium
evaluated
by
use
of dyr
bases,
metal
not Of
bands.
used
be
different
be
of
2
with
intensive Ray
the
orbitals,
corresponding
constants of
the
or
p
success
in
charge-trans-
for
process
spectral
The
this
reason
(se8 methods
eq.1
3.10 TABL_E
spectra
Electronic
1
of Ni(I1)
bisidithiophdsphate.
in different
E1
Solvent
solvents
(in
E2
E3
complexes
cm -9
Ref.
benzene
74
SDII
19 200
26 000
192
p yridine
0
550
9 000
14 900
192
21 834 21 600
2
12 820
d-picoline
13
0 -picoline $-picoline 1.
3
8 550
9 810
14 930
2
8
9 010
14 930
2
550
This paper
2. H.E. Franics,
G.L. Tincher,
G.Pl. Woltermann 3, R,L, Carlin,
orbitals the
850
of the bases,
corresponding
molecules electron
wil1 be more
hiqh
IO,
Losee - Inorg.
2620
Chem.,
J, R.
orbitals
in axial
the electron
Wasson,
(1971) 2, 2084 (1970)
and d,, and dyz orbitals
e or x
coordinated donors,
Chem.,
- Inorg,
O.B.
W.F. Wagner,
interact
from the bases.
position transfer
than that through
Since
of the complex through
donor
the acceptor's
with the
are fiv bonds
5
-dative
bonds, Now we vi13
consider
our attention
namely,
uhen two electrons
(Ni(I1)
and Cu( II) complexes),
this
orbital
lied orbitals, Cu(II)
( Ca(I1)
are located and
complekes),
in all studied
), they are filled,
when
Since here
to two typical
cases,
on the d,2 orbital one
electron
occupies
the dXz and dyz are low
complexes
(
Co{
II), Ni(II),
111
6.2
Metal complex
Fig.3
Donor molecule
Axial
interaction
between
and the appropriate .
In Ni(I1)
planar
orbitals
chelate
complexes
when one or two base molecules
the 5 axis,
the ground
state OP NiL28,
(b2g)2(a,,)'(b,g)'~
and the complex
can be registrated
by use of magnetic
tion
[2, 6, 73 , that
in Cu(II)
of the base molecule
electron
transfer
Prom the
state
is
are diamagnetic.
are coordinated
along 4 ( x = 1 or 2) is (e,)
becomes
paramagnetis,
spectral
chelates
( or molecules filled
dyr orbitals
the ground
methods
by the use of magnetic
It was established, methods
dr2, dxZ,
from the base molecule
and the complexes
(eg)4(b2g)2(a,g)2(b,g)o However,
the metal
dZ2 orbital
[4,53 .
spectral
the axial
) reeults
which
coordina-
particular
to the dX:2_
Y2
112 arbital,
on which
the unpaired
case the complex rhombic
becomes
distortion
the electronic
expended
in this
structure
corresponding
changes
unpaired
in Table
Since complexes
nuclei
the unpaired
magnitudes pK
in the electronic the decreasing
u,with Some
of the
of the
the magnetic data about
for some copper
electron
in Co(I1)
on the d,2 orbital,
of bases
is observed
with
nuclei
these
complexes
2,
is located
coordination
in
EPR parameters*,
interaction
(shf)
ligands.
in the shf interaction
are given
shf interaction
planar
as a result
with
chelate of axial
their magnetic
[9 - 131 . It was established
of this shf interaction
is in some
also that the
correlation
with
values.
*Since nated
chelate
changes
of their
is for example
in the plane
and some
are conected
changes
of the superhyperfine
from the equatorial
their
of these
electron,lies
changes
complex
In this
x,
is obtained--The
in the magnitudes
of the complex
magnitudes
is located,
in the plane
plane
of the
The mosr. clear evidence structure
electron
the exchange
between
the coordinated
state of the metal
complex
is very fast (see below),
results processes
have
been obtained
of coordination
the complex molecules
in solution
in the solid
by using
the analogy
of base molecules and selfassociation
state,
and noncoordi-
between
along
the
the taxis
between
and the observed
these of
compfex
equality
in the
shape and parameters of the EPR spectra in both cases i72 . Here we wish to note that some autors have no success in simulating the
theoretical
until
assuming
coordinated
EPR spectra rhombic
complexes
coinciding
distortion 681
.
with
the experimental,
in the plane
x~ of the
113
TAELE2 The
influence
Cu(ox)2, of
the
of
Cu(tox)2, s.h.F.
Base*
Complex
cdox)2
axial
coordination
and
Cu(dmg)2
interaction
A,,
with
+O.SG
of
base
complexes the
on
2
chelate
ligands
(G)
A,
13.5
10.5
11.5
0.8
PY
11.8
9.2
10.1
0.7
qu
11.3
8.8
10.1
0.6
.-qu
12.4
9.6
10.5
0.7
IMFA
11.4
8.8
9.7
0.7
Tht
13.3
10.3
0.8
11.3 TO.9
16.2
13.0
14.1
0.9
PY
15.7
12.5
13.5
0.8
qu
15.7
12.6
13.5
cl.8
DRFA
15.3
11.9
13.0
0.8
PY H2°
DMFA
along
magnitudes
Aiso(G I
AL-+0,5G
13.5
Diox
Cu(dmg)2
the
equatorial
Iiox
cu(tox)
rroleculss
19.3
15.9
17.0
0.9
18.6
15.3
16.4
0.9
18.5
15.6
16.6
0.9
*
PY - pyridine;
-
dimethylformamide;
qu
- quinoline; THt
-
i-qu
Thiophane;
-
iso-quinoline;
Diox
-
dioxane.
114 In most metal
cases
complexes
the axial
coordination
is equilibrium
process
of bases
to the
Cl - 37 :
% MeLx + B a-
meL,.B
(1)
Ir;! PieL .,B and the equilibrium use of different procedire
+
spectral
is given
the
type
of
IrieLx.B2
k, and 5 can be estimated by -2 methods ( for electronic spectra the
in fi41 9 or for EPR
lc,77g2,
( metal
given pK
of _, k obtained
complex
values
of
by studing
and different the
bases
was
bases found
TABLE -pk
values
(at 25OC)
of
some Lewis
or
Base
pK*
Comparing
the between
no good correlation .
The
with the
pK data for some
bases
and equilibrium
CuL2 + B 7
dithiocarbamate)
in
constants
CuL2.B CHC13
Cu( acac)2
(
cl71
.
Cu(
dt c) 2
5-11 + 5.34
2.95
o-17
i-quinoline
5.36 + 5.42
2-30
0.18
quinoline
3.97 + 4.96
0.48
0.029 0.06
thiophate
-5.10
+ -4.52
O-28
dioxane
-4.3
+ -2-92
O-27
organic
from D-D,
bases
Perrin
in aqueous
"Dissociation
solution”,
London,
constants
k -1
L =
pyridine
*Data
a
3
for the reaction
acetylacetonate
separetely),
the interaction
[16,17]
- in
of k, depends
and ligand
of the bases.
as well as on the properties magnitudes
and NMR spectra
and the magnitude
complexes
the
(2)
constants
6'151 )- In all cases on
B 4
of
Butterworths,
1965.
115 Lewis
bases
copper
and the corresponding complexes
The acceptor important
are shown on Table properties
for the values
112' In copper chromophores
chelate in which
> Cu(02N2)
The acceptor
Lewis
7 Cu(N4)
bonds
character
increases,
on the metal
of the
p
in the
interac[2]
:
7 Cu(S4)
7 Cu(Se4)
decrease
in this order.
in this order
and therefore,
order
k and -1 of the
has been established
>Cu(N2S2)
that
are
constants
of k, decrease
of the complexes
Howe#:er, it is well known, the covalent
complexes
the following
base
for two
3.
of the equilibrium
the values
properties
of k, obtained
of the metal
complexes
tion with one and same Cu(O4)
values
of chromophores
-metal-equatorial the remaining
ligand
positive
charge
ion decrease.
The properties the magnitudes
of the solvents
of the equilibrium
of the specific
solvatation
are also
constants
of the base,
important
for
k, and =2' k because
and that of the
complex[l6,1]. Since the forward
the equilibrium (5)
it is possible NMR.
The
changes
and the backward to obtain
values
of $
11, is the
(&)
rate
and/or
k+, could
ratio
between
constants
of (I),
by the use of EPR
its magnitude
in the line width
coordination.
constant
be estimated
in the corresponding
and
from the
spectra
due to
For the reaction kf Cu(dtc)2
+ B _T
Cu(dtc)2.B
(3)
-b when B = pyridine k& = 0.37x10
9 set -'
Valuable structure
&
= 2x10
9
set -1 , and when I3 = piperidine
-
c78 3 .
information
of the bases
about
induced
the changes
by their
in the electronic
coordination
along
the
116 f, axis of the metal netic
in PMR
shifts
to
223 . This bonds
the
found
to decrease atom
and undependent the ring
the paramagnetic
-system
X7
of the heteroatom.
of the paramsgnetic in axial tional
position
to their
chelate
is coneected
spectral
properties.
ligands interest several
since orders
complexes
than
with monodentate
of the base
distortion
and expansion
possibility
for opening
of these
of the complex of the chelate
on Fig.4.
the equatorial
in the following
of the bases propor-
of the metal
changes
in their
of menodentate is of special complexes
constants
It was suggested
as a first
ted. The scheme
explained
complexes
of this process
of the base
Formaly,
electron
are in general
the corresponding
way and the coordination is shown
the
that the magnitudes
of coordination
constants
(or bases)
are equal
and therefcire, in their
ligands.
that the mechanism
6, 261, nation
higher
and aroma-
G 23 - 251,
in the plane XJ
of the chelate
the stability
-
_
structure,
=
r-
with
with considerable
The problem
in the plane
on the
of all protons
complexes,
of Lewis bases
and electronic
619
in the molecule
c24,25]
of the
metal
due to the coordination
to the metal
geometry
the
like aniline
It is established,
pK values
complexes
shifts
piperidine,
increasing to
is superconjugated
shifts,
Coordination
with
bases
position
The paramag-
like pyridine,
delocalization
In conjugated
of their
by MR.
coordinated
is due of the electron
tic phosphines
pair
of bases
functional
of the bases.
since
are abtained
spectra
etc, were
quinoline, distance
complexes
includes
of the
recentlyr2, axial
step providing
coordi-
rhombic
in the plane x~_. The ring
is increased
in the plane x~
coordination
way /Fiq,S/:
are in
in this
is facilita-
of the base
If we consider
could be the
117
Fig.4
FSechanism to the
of
equatorial
metal
chelate
(A)
coordination
%a- I-
= l/2
x2
+
molecule
d,2_Y2)
1
XYZ
piz-
base
ICI
( dz2_
-
xy2
the
complex
(a, 2
of
dz2_ x2
2
%2_ Y2 dz2_
Y2
dXz dXY dXZ
Fig.5.a)
Transformation
metal b)
chelate
Changes
upper
species axial
base
after (A
in
will originate molecule
The
xyz
coordinate
into
XYZ
(see
of
the
metal
signs
system
the
of
the
text).
orbitals
dck
to the
transformation
position
A
the
complex
in the
obtained
x/2
of
new
xy~ , but only
coordination Fig.5),
of
rotation
position
B on Fig.5.
in the
plane
coordinate
system
XYZ
axes
are
rotated
base
around
is situated
the
the
molecuke
the
in
x or 1
axis
In this
position
XY* -
and
two
of
have
the
same
with
z/2.
the
centrum
in the
donor
as
118 the
~c01;i.sProm
back
to
the
nated
on
state
C will
the
state
this
Powewer, go
chelate
the
is
state Z
dZ*_
the
be
r* =
the
ortsitals
the
dx2
_
d,2_
the
base
molecules
position, plane
as
are well
Evidence of
x~
splitting
due
Typical
example
stable since
arbitrary The
d,*_
are
Y2
to
having
ortlital
y*
fully
that
for
of
to
planes
the
on
case
the
are
rotation
shown
the of
plane
equivalent
The
orbitals
applied
(4)
their
another).
met21
)
Fig.5',
when
two
complex
bidentate
will
traasbase
in
place. coordination the
case
EPR
of
magnetic
coordination
in the
plane
x~
in the!_r EPR
effective
overlapping
the metal.
reaction
-
+
one
interaction
splitting
and
x*
cooroination
give
this
the
coordi-
the
spectra
the
nuclei
are
of
in the
bases
in which
shf
unpaired
electron,
from
bases
the
copper(I1)
chelate
lying
occurs, complexes
.
The bases
for
will
is possible
complex.
in the
takes
the
axis.
atoms
2nd
cboosen
fact
be
equatorial
the
with
plane,
307
when
complexes
to
in this
c 26 -
as
XY -
procedure
the
the
coordinated
for
the
of could
position
in cis-
plane
(normal
method
oonor
been
d,2
2nd
transformation
Analogous
chelate olane
(1/2P(d,*_
excluding
perpendicular
complex
on
2s:
x2
y2 orbital
the
starting
represented
and
provide
the
therefore
the
has
Xyz
1.
the
The upper
of
d~2_
mutually
one-of to
the
situate0
end
move
System
geometry
can
r2
will
realized.
be
are
unstable,
A, or
axis
coordination
in mind
ligands
are
of of
molecule
the
complexes
spectra
have
between
Therefore,
performed
the
and
21
conditions , and
molecules) the
provided
the orbitals
some
131,
(or
of
existence
the
the of
existence
shf of
of the base molecule for
electron
oxidation-reduction transfer
is possible
119
depending
on the reagents
of piperidine plex
shows
have
been
with
copper
with
copper
equatorial
and other
-thiooxines, chelste
comreaction
interacts
-dithiocartamates,
lignnds,
the redox
-di-
reaction
place 1 2, 263.
take
Wetal
chelate
interact
complexes
with
they
will
could
be@
other
atoms of the ligand
donor
metal
atoms
chelates
acceptor
molecules
the spectra shows
during
obtained
Gr, NO3r ClG4)
molecules
magnitude
the
of mixed-figand
to the changes the
gives
in the
and for
complexes by the
complexes.
of the type bis( X = Cl,
, C(kG2),
isotropic
the presence nuclei
g-values of
in
fig.6
copper
6353
for the suggested
of
and
chsnges
such like CuX2
and 7Q98'8r
between
formation
complexes
and SbGr3
hf interaction,
the evidence
the
between
and acceptord
conplex,
complex&s,
chelate
followed
c32 - 343, SnCl4
of
results
interaction
centers
system,
and the resulting
due to one 3%37Cl,
splitting
metal
donor
The inters&ion
or charge-transfer
conviniently
complexes
In addition
spectra
is
ion.
and therefore,
of the
j't -eronatic
metal
between
EPR spectra
dithiocarbamate
etc.
the
of the starting
several
CuXdtc
-
or its
and acceptor
The interaction
The
molscules.
from the chronophore
mixed-ligand
modificated,
act also as donors
acceptor
complexes
Co( II) planar
the
interaction
but redox
of the base,
when the same base
However,
bis-oxines,
thiophosphates,
the
bis-hexsfluoroacetylacetonzte
coordination
not observed.
Far example
propertiEs,
the
kO26363, end shf
in the EPR
mixed-ligand
structure*,
*In the solid r3.73 *
state
these mixed-ligand
complexes
dimerized
120
I
Fig.6
I
EPR
I
spectra
interaction Cu(N03)2
I
of mixed-ligand of Cu(dtc)2
cux* the presence
was established
The EPR spectra ligands from
of the
are shown
between
obtained
CuC12
(b), CuBr2
complexes
of the solvent's
complexes
containing
35.37 Cl and 7g*81 Fir nuclei
and
contain-
and one dithiocarbamate
depending
where
the
(c),
bis-dithiocarbamates
copper(I1)
(or bromine)
in Fig.7
during
(e>
Ni(I1)
of mixed-ligand
ing one or two chlorine ligand
(a) with:
(d), and CU(C~O~)~
In the reaction
complexes
well could
properties
c383
one and two halogen
resolved
shf splitting
be easily
recognized.
121 NI
NI (dt+
(dtc12 + CuX2 (X=CI, Er)
.
.
Cuxdtc
[CuX,dtc-j-
Fig.7
a -X=Cl
c-Y-N4
a-X=Cl
b-X=Br
d - Y = ClO,
b-X=Br
EPR
spectra
during (b), right
the
of
mixed- ligand
interaction
CU(NO~)~ -
+ CU*+-----
( Y = q,
(c),
in acetone
of
CU(C~O~)~ or
[cu WtG] + c-Y=NCL, d - Y = CIO,
copper(I1) Ni(dtc)2 (d),
equivolume
ZY-
C104)
complexes
with:
CuC12
left
column
mixture
of
obtained (a),
CuBr2
in DMFA EtOH
and
and CHC13
122
The interaction proceeds
as a redox
Special Pt(II),
of these
is shown
is formation
there
The
433.
a charge-transfer
These
have
teen
bases,
x-aromatic
oxines,
X-acceptors
etc.
which
spectra
conclusions also
by
etc.
precipitates
r39 -
of the precipitate band,
system
attributed
of the ligands
for the formation X-ray
in
as tetra-
tetracyanoquinodimethane,
;z‘ -d onor
conFirmed
nickel(II),
containing
of a new absorption
from the
;;C-acceptor.
complex
schiff
with
electronic
shown the presence
acids
copper(
with ligands
complexes
Lewis
.
of a new compound
reflectance
with
toward
trinitrobenzene,
cyanoethylene,
the
c353
complexes
etc.
complexes
such like salicylaldehydes,
the reaction
have
reaction
interest
Pd(I1)
system
of some
analysis
to to
of CT
644
-
497
9).
(Fig,
It was shown coordinate
that Co(I1)
Lewis bases
es are effective
oxygen
coordinated
along
lished
also
along
properties,
ligandsl50,
511
effective
oxygen
chelate
the f axis,
carriers
complexes
However,
and the oxygen
these
of the 02 binding
can complex-
molecule
the L axis of the complex.
that the reversibility
on theredox
planar
is
It was estabis dependent
e.g. of the shape of the equatorial
, and it is assumed carriers
that at the moment
are the Co(I1)
bis-schiff
the most
base
complex-
es &!52,533 . The interaction Lewis
acids
regulation solvent
and/or of their
bases
plays
activity.
reagents,
interaction
Thus,
chelate
an important In most
on the rate of the chemical
to the specific the
of the metal
between
cases
complexes
role for the the influence
reactions
of the
can fie attributed
the solvent
the rate of the reaction
with
molecules
between
copper
and
123
Charge-transfer
band
energies(cm-')+
+AS Bolley.R L P Wllllams.J Dwrlght-J Chem Sot. 2579 (1965) Fig.8
Schematic
representation
complexes
and
chelate
complexes
more
than
weak
Lewis
during
the
peroxides fact
be
coordination equatorial 1 igands
and
c!i4]
reaction are
can
chloranil
some
3 - 4 orders bases
are
.(The
remains
explained
plane
the
organic
increased.
the
hydroperoxydes OF
that
as
complex
donor
the
the this
a result
metal
organic
of ion hydro-
experimental of
the
extended
properties
between
(1:2)
quaotitis
of
becomes
interaction
Me(ox)2
increases
small
state
acceptors,
the
between
trinitrobenzene
unchanged.)Since
therefore, The
and
oxidation
assuming
and
complexes
presence
strong
base,
CT
(1:l)
in the
relatively
of
of
halogen
axial in the
of
the contain-
124 ing hydrocarbons sence
or’
1553
.
are
weak
weak
Lewis
bases
It is well
known,
Lewis
structure
acids the
OF
the
ced,
and copper
react ion
could
and
takes
mixeo-ligand
be
do
not
induce
but
if
place
in
any
weak
and
complexes
The application
explained
OF different
acceptor
metal
complexes
wide
of the fine mechanism reactions. be extended
bases
spectral
of the donor-and/or discovers
in the are
introdu-
stage
of the
formed.
investigation chelate
pre-
mannier
same
changes
Lewis
the
hydrocarbons
in the initial
are
in
the
that halogen-containing
complexes,
reaction
complexes
bis-chelate
of difFerent
methods
properties
sources
chemical
In view of this the studies
on the of the
for understanding
and biochemical
in this
direction
will
in future.
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