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Complexes with ligands containing nitrile groups XVII the ligand properties of some dinitriles
INORG.
NUCL
CHEM. LETTERS
VoL
11,
pp.
35-39,
1975.
Pergamon
Press. Printed
in
Great
Britain.
COMPLEXES WITH LIGANOS CONTAINING NITRILE GROUPS XVII * THE LIGANO PROPERTIES OF SOME OINITRILES. A.P. Zuur, Miss P.L.A. Eversteijn and W.L. Groeneveld. Oepartment of Inorganic Chemistry,
State University, P.O. Box 75,
Leyden, the Netherlands.
~ece~edlOSep~m~r1974) A number of metal-chloro-antimonate
solvates is reported containing the ligands
succino nitrile (an), terephtalo nitrile [tn) and dodecane dinitrile [dn).The formulas are: M(II)(sn)3[SbCl6) 2 and M[II)(tn)6[SbOl6) 2 in which M is Co and Ni; M[ll)(dn)3(SbC16) 2 in which M is Co, Ni and Cu. Ligend field and infra red spectra indicate regular oetahedral coordination of the ligands around the M(II) ions, only in the case of the Cu[II) ion a slight distortion of this symmetry is found.
In
previous
with
communications
linear
organic
These ligands the of
length
nickel-,
the metal
these
ligands,
ions
are
Only the
tetrahedral
of the
zinc
[IV]
two nitrile
between the
[4)
completely
complex
of metal
as m o n o d e n t a t e
chain
chloride
not
adducts
containing
can b e h a v e a p p a r e n t l y
which
a complete
molecules
and s t r u c t u r e
calcium-,
[1,2,3)
and s i l v e r
and m e t a l
groups
two n i t r i l e
ortho-coordinated
of four
C~N g r o u p s
depending
groups. [5]
are reported,
reported
around
on
Adducts
by t h e C~N g r o u p s
~u[N~C-(CH2J2-C~N] 9NO 3 is
coordination
halides
h a v e been r e p o r t e d .
and b i d e n t e t e
nitrate
(V)
in
in of
which
t h e Cu i o n
occurs
[6].
Part XV.C.O. Jansen-Ligthelm, 7, 113 [ 1 9 7 3 ] .
W.L. Groeneveld and J.Reedijk,Inorg.Chem.Acta,
Part XVI. A.P, Zuur, Niss P.L,A, Eversteijn, B.T.de Groeneveld, Inorg.Nucl.Chem. Letters 10, 213 [ 1 9 7 4 ] ,
35
Haas, A . W i l l e m s e
end W.L.
36
THE L1GAND PROPERTIES OF SOME DINITRILES
In this trile
investigation
ligand
(tn) and dodecane
properties
dinitrile
of succino
Vol. 11, No. 1
nitrile
(dn) are studied
[sn),
terephtalo
in a complete
M2~ion
ni-
nitrile
solvation.
Experimental. The complexes
were
synthesized
SbCI 5 as c h l o r o - a c e e p t o r
by stirring
in an excess
M C I 2 : S b C I 5 = 1:2. After
filtering
nitro methane
[M(CHIN02]6]
6 moles These
solvate,
of the 3igand
crystals
were
were determined plexes
complexes
isolated
the diffuse rence.
Infra
as nujol
between
lours.
are listed
They are all
The CsN stretching pon coordination gen
(9).
obtained culated
from the
with
in the infra
OR-2A
with
chloride
I cm
chlorine
Elmer
molar
(7]. After
ratio
of the adding
[M(L) 3 or 6](SbC16)2 The metal contents
spectra
instrument
with
a solution
in vacua.
field
a PerKin
accuracy
contents
of the com-
were recorded
by
using MgO as a refe-
225 s p e c t r o p h o t o m e t e r
-I
and Discussion. I together
of the
with
ligands
the geometry spectra.
are listed
symmetry
the ligand
red region.
[lJ, despite
Ligand
(Table
The band maxima
succino
III.
the presence
nitrile
length of the
sensitive
data and coto moisture.
IIJ all show an increase
of the ligands
in Table
analytical
u-
via the lone pair of the nitro-
for the species;
The
their
but very
Known for e Londing
field
(10,11]
from octahedral
In the complexes
chelation
about
ligand
parameters
viations
found
is well
Information
method.
at r o o m - t e m p e r a t u r e
frequencies
as
(8).The
on a BecKman
in Table
stable
and dried
chlorides
for 24 hours;
of the composition
titrations
plates,
Results The compounds
separated
were obtained
CsBr
metal
metal
. (SbCIB] 2 was obtained
by filtration
method
red spectra
mulls
-2 +
by Volhard's
reflectance
of nitro methane
the remaining
by complexometric
were determined
the divalent
around
the M 2+ ions was
assignments
The spectra M2+[L)3
and the cal-
do not show de-
and M2+(L]6 .
(sn) only one shifted
of this molecule large anions
is too short
SbCI~u
YC~N
is
to give
in the lattice
Vol. 11, No. 1
THE LIGAND PROPERTIES OF SOME DINITRILES
37
this ligand seems to act as a bridging agent between two q 2+ ions. Replacing oino nitrile by the larger and rigid molecule tereptalo nitrile ing-capacity
has disappeared.
suc-
(tn] this bridg-
In the infrared region the YCeN of the free ligand
is still present indicating that only one C~N group is involved
in the coordina-
tion of the species M 2+ [tn] 6. The presence of two higher shifted CeN frequencies is no doubt originated
by symmetry effects,
caused by ligand coordination
symmetry.
TABLE I Oinitrile complexes, Complex
analyses and colours.
M 2+
Sb
CI
Colour
Cale.
Found
Calc.
Found
Calc.
Found
2+ Ce[sn] 3 [SbCl6] 2
6.08
6.13
25.2
25.1
44.0
43.8
pink
Ni(sn] 2+ 3 [SbCl~] 2
8.08
5.84
25.2
25.1
44.0
43.7
blue
Co[tn] 6 (SbCl6] 2
3.92
4.08
16.2
16.9
28.5
30.6
pink
Ni[tn] 2+ 8 ( SbCI~] 2
3.92
3.84
18.2
16.2
28.5
28.4
blue
Co[dn] 3 2+ (SbCl~] 2
4.52
4.46
18.7
18.4
32.6
33.0
pink
Ni(dn] 2+ 3 [SbCI~) 2
4.52
4.48
18.7
17.2
32.8
32.0
blue
Cu[dn)32+ ( SbCI6 )2
4.85
4.76
18.6
18.5
32.5
33.4
green
2+
sn=succino
nitrile NC-[CH2]2-CN,
tn=terephtaio
dinitrile N C C P C N ,
dn=dodecane dinitrile NC-[CH2]Io-CN.
TABLE II Streching frequency Compound succino nitrile
in dinitrile complexes
YCN
in om-1[* I cm -I)
Compound
2260
dodecane dinitrile
YCN 2246
Co2+[sn]3[SbClB]2
--
2293
Co2+[dn]3[SbCl6]2
--
2284
Ni2+(sn]3(SbCl6]2
--
2295
Ni2+(dn)s(SbCl6]2
--
2288
Cu2+(dn]3[SbC16)2
--
2271 2289
terephtalo dinitrile 2234 Co2+(tn)6(SbC16)2
2234,2268,2278
Ni2+(tn)G(SbCl~)2
2234,2265,2275
or site
38
THE L1GAND PROPERTIES OF SOME DINITRILES
Vol. 11, No. 1
TABLE III Ligand Field Maxima [kK) and calculated parameters (cm-1).
Parameters (accu-
Maxima with assignments Compound
-1 racy 5-10 cm )
(accuracy 0.1 kK) 4TqgiP)~--4Tlg iF)
4T294__ 4TlgiF)
Dq
B
Coisn)~+(SbC16)2
9.7
20.8
1060820
Coitn]~+iSbC16)2
9.5
20.8
1040840
Coidn)~+[SbCl6)2
9.5
20.8
1040830
3T2~-- 3A2g
1Eg~--3A2g
3T1 g iF )~--3A 2g
3TlgiPLE-3A2g
Niisn)~+iSbCl6)2
10.9
14.2
17.7
*
1090950
Niitn)~+(SbC16)2
10.6
14.2
17.2
*
1065930
Niidn)~+(SbC16)2
10.7
14.2
17.3
*
1075965
* Obscured by SbCI6 absorptions.
In the complexes containing dodecane dinitrile
(dn) as the ligand, no YC~N
of non-bonded nitrile occurs in the infra red region, indicating that this ligand acts as a bidentate.
It is remarkable that these complexes were ob-
tained as crystalline precipitates. From the size and shape of this ligand one would expect liquid or amorphous products with low melting points. The two shifted nitrile frequencies in the copper complex indicate a static or dynamic O4h distortion from the octehedral symmetry as found previously
(12,13). In the complexes Midn) 2+ 3 [ SbCl~) 2 several b r i d g i n g
or c h e l a t i n g
may be r e a l i z e d .
in our l a b o r a t o r y
t h i s problem.
X-ray i n v e s t i g a t i o n s
are started
structures to solve
Vol. 11, No. 1
THE LIGAND PROPERTIES OF SOME DINITRILES
39
References.
I.
M.S. GILL,
H.S. AHUJA and G.S. RAO, I n o r g .
2.
O.M. BARNHART, C.N. CAUGHLAN and MAZHAN UL-HAQUE, I n o r g .
3.
S.C. JAIN and R. RIVEST, Can. J . Chem. 41,
2130 (1963)
4.
J.L.
Chem. A c t a 4,
5.
MASAKO SUZUKI and TAKEHIKO SHIMANONCHI, Bull. Chem. Soc. Japan 41, 2353 (1968)
6.
Y. KINOSHITA, I .
7.
W.L. DRIESSEN and W.L. GROENEVELD, Rec, T r a y . Chim. 88,
8.
C. SCHWARZENBACH, Die K o m p i e x o m e t r i s c h e T i t r a t i o n , F. Enke V e r l a g , S t u t t g a r t 1965
9.
K.F.
BURMEISTER and M.Y. AL-JANABI,
Inorg.
Chim. Acta 7, 359 (1973)
MATSUBANA and Y.SAITO, B u l l .
PURCELL, J. Am. Chem. Soc. 89,
101
J. REEDIJK, P . W . N . M . v .
11.
J,
12.
A.P.
13.
C.D. JANSEN-LIGTHELM,
Chem. 7, 1135 (1~68)
581 (1970)
Chem. Soc. Japan 32, 741 [1959) 491 [1969)
247 (1967)
LEEUWEN and W.L. GROENEVELD, Rec. T r e y . Chim. 67, 129 (1968)
REEDIJK, W.L. DRIESSEN and W.L. GROENEVELD, Rec. T r a y . Chim. 88, 1095 (1969) ZUUR, A . H . L .
REINTJES and W.L. GROENEVELD, Rec. T r a y . Chim. 89, 385 (1970) W.L. GROENEVELU and J. REEDIJK, Part XV, I n o r g . Chim. A c t a 7, 113 (1973)
NUCL
CHEM. LETTERS
VoL
11,
pp.
35-39,
1975.
Pergamon
Press. Printed
in
Great
Britain.
COMPLEXES WITH LIGANOS CONTAINING NITRILE GROUPS XVII * THE LIGANO PROPERTIES OF SOME OINITRILES. A.P. Zuur, Miss P.L.A. Eversteijn and W.L. Groeneveld. Oepartment of Inorganic Chemistry,
State University, P.O. Box 75,
Leyden, the Netherlands.
~ece~edlOSep~m~r1974) A number of metal-chloro-antimonate
solvates is reported containing the ligands
succino nitrile (an), terephtalo nitrile [tn) and dodecane dinitrile [dn).The formulas are: M(II)(sn)3[SbCl6) 2 and M[II)(tn)6[SbOl6) 2 in which M is Co and Ni; M[ll)(dn)3(SbC16) 2 in which M is Co, Ni and Cu. Ligend field and infra red spectra indicate regular oetahedral coordination of the ligands around the M(II) ions, only in the case of the Cu[II) ion a slight distortion of this symmetry is found.
In
previous
with
communications
linear
organic
These ligands the of
length
nickel-,
the metal
these
ligands,
ions
are
Only the
tetrahedral
of the
zinc
[IV]
two nitrile
between the
[4)
completely
complex
of metal
as m o n o d e n t a t e
chain
chloride
not
adducts
containing
can b e h a v e a p p a r e n t l y
which
a complete
molecules
and s t r u c t u r e
calcium-,
[1,2,3)
and s i l v e r
and m e t a l
groups
two n i t r i l e
ortho-coordinated
of four
C~N g r o u p s
depending
groups. [5]
are reported,
reported
around
on
Adducts
by t h e C~N g r o u p s
~u[N~C-(CH2J2-C~N] 9NO 3 is
coordination
halides
h a v e been r e p o r t e d .
and b i d e n t e t e
nitrate
(V)
in
in of
which
t h e Cu i o n
occurs
[6].
Part XV.C.O. Jansen-Ligthelm, 7, 113 [ 1 9 7 3 ] .
W.L. Groeneveld and J.Reedijk,Inorg.Chem.Acta,
Part XVI. A.P, Zuur, Niss P.L,A, Eversteijn, B.T.de Groeneveld, Inorg.Nucl.Chem. Letters 10, 213 [ 1 9 7 4 ] ,
35
Haas, A . W i l l e m s e
end W.L.
36
THE L1GAND PROPERTIES OF SOME DINITRILES
In this trile
investigation
ligand
(tn) and dodecane
properties
dinitrile
of succino
Vol. 11, No. 1
nitrile
(dn) are studied
[sn),
terephtalo
in a complete
M2~ion
ni-
nitrile
solvation.
Experimental. The complexes
were
synthesized
SbCI 5 as c h l o r o - a c e e p t o r
by stirring
in an excess
M C I 2 : S b C I 5 = 1:2. After
filtering
nitro methane
[M(CHIN02]6]
6 moles These
solvate,
of the 3igand
crystals
were
were determined plexes
complexes
isolated
the diffuse rence.
Infra
as nujol
between
lours.
are listed
They are all
The CsN stretching pon coordination gen
(9).
obtained culated
from the
with
in the infra
OR-2A
with
chloride
I cm
chlorine
Elmer
molar
(7]. After
ratio
of the adding
[M(L) 3 or 6](SbC16)2 The metal contents
spectra
instrument
with
a solution
in vacua.
field
a PerKin
accuracy
contents
of the com-
were recorded
by
using MgO as a refe-
225 s p e c t r o p h o t o m e t e r
-I
and Discussion. I together
of the
with
ligands
the geometry spectra.
are listed
symmetry
the ligand
red region.
[lJ, despite
Ligand
(Table
The band maxima
succino
III.
the presence
nitrile
length of the
sensitive
data and coto moisture.
IIJ all show an increase
of the ligands
in Table
analytical
u-
via the lone pair of the nitro-
for the species;
The
their
but very
Known for e Londing
field
(10,11]
from octahedral
In the complexes
chelation
about
ligand
parameters
viations
found
is well
Information
method.
at r o o m - t e m p e r a t u r e
frequencies
as
(8).The
on a BecKman
in Table
stable
and dried
chlorides
for 24 hours;
of the composition
titrations
plates,
Results The compounds
separated
were obtained
CsBr
metal
metal
. (SbCIB] 2 was obtained
by filtration
method
red spectra
mulls
-2 +
by Volhard's
reflectance
of nitro methane
the remaining
by complexometric
were determined
the divalent
around
the M 2+ ions was
assignments
The spectra M2+[L)3
and the cal-
do not show de-
and M2+(L]6 .
(sn) only one shifted
of this molecule large anions
is too short
SbCI~u
YC~N
is
to give
in the lattice
Vol. 11, No. 1
THE LIGAND PROPERTIES OF SOME DINITRILES
37
this ligand seems to act as a bridging agent between two q 2+ ions. Replacing oino nitrile by the larger and rigid molecule tereptalo nitrile ing-capacity
has disappeared.
suc-
(tn] this bridg-
In the infrared region the YCeN of the free ligand
is still present indicating that only one C~N group is involved
in the coordina-
tion of the species M 2+ [tn] 6. The presence of two higher shifted CeN frequencies is no doubt originated
by symmetry effects,
caused by ligand coordination
symmetry.
TABLE I Oinitrile complexes, Complex
analyses and colours.
M 2+
Sb
CI
Colour
Cale.
Found
Calc.
Found
Calc.
Found
2+ Ce[sn] 3 [SbCl6] 2
6.08
6.13
25.2
25.1
44.0
43.8
pink
Ni(sn] 2+ 3 [SbCl~] 2
8.08
5.84
25.2
25.1
44.0
43.7
blue
Co[tn] 6 (SbCl6] 2
3.92
4.08
16.2
16.9
28.5
30.6
pink
Ni[tn] 2+ 8 ( SbCI~] 2
3.92
3.84
18.2
16.2
28.5
28.4
blue
Co[dn] 3 2+ (SbCl~] 2
4.52
4.46
18.7
18.4
32.6
33.0
pink
Ni(dn] 2+ 3 [SbCI~) 2
4.52
4.48
18.7
17.2
32.8
32.0
blue
Cu[dn)32+ ( SbCI6 )2
4.85
4.76
18.6
18.5
32.5
33.4
green
2+
sn=succino
nitrile NC-[CH2]2-CN,
tn=terephtaio
dinitrile N C C P C N ,
dn=dodecane dinitrile NC-[CH2]Io-CN.
TABLE II Streching frequency Compound succino nitrile
in dinitrile complexes
YCN
in om-1[* I cm -I)
Compound
2260
dodecane dinitrile
YCN 2246
Co2+[sn]3[SbClB]2
--
2293
Co2+[dn]3[SbCl6]2
--
2284
Ni2+(sn]3(SbCl6]2
--
2295
Ni2+(dn)s(SbCl6]2
--
2288
Cu2+(dn]3[SbC16)2
--
2271 2289
terephtalo dinitrile 2234 Co2+(tn)6(SbC16)2
2234,2268,2278
Ni2+(tn)G(SbCl~)2
2234,2265,2275
or site
38
THE L1GAND PROPERTIES OF SOME DINITRILES
Vol. 11, No. 1
TABLE III Ligand Field Maxima [kK) and calculated parameters (cm-1).
Parameters (accu-
Maxima with assignments Compound
-1 racy 5-10 cm )
(accuracy 0.1 kK) 4TqgiP)~--4Tlg iF)
4T294__ 4TlgiF)
Dq
B
Coisn)~+(SbC16)2
9.7
20.8
1060820
Coitn]~+iSbC16)2
9.5
20.8
1040840
Coidn)~+[SbCl6)2
9.5
20.8
1040830
3T2~-- 3A2g
1Eg~--3A2g
3T1 g iF )~--3A 2g
3TlgiPLE-3A2g
Niisn)~+iSbCl6)2
10.9
14.2
17.7
*
1090950
Niitn)~+(SbC16)2
10.6
14.2
17.2
*
1065930
Niidn)~+(SbC16)2
10.7
14.2
17.3
*
1075965
* Obscured by SbCI6 absorptions.
In the complexes containing dodecane dinitrile
(dn) as the ligand, no YC~N
of non-bonded nitrile occurs in the infra red region, indicating that this ligand acts as a bidentate.
It is remarkable that these complexes were ob-
tained as crystalline precipitates. From the size and shape of this ligand one would expect liquid or amorphous products with low melting points. The two shifted nitrile frequencies in the copper complex indicate a static or dynamic O4h distortion from the octehedral symmetry as found previously
(12,13). In the complexes Midn) 2+ 3 [ SbCl~) 2 several b r i d g i n g
or c h e l a t i n g
may be r e a l i z e d .
in our l a b o r a t o r y
t h i s problem.
X-ray i n v e s t i g a t i o n s
are started
structures to solve
Vol. 11, No. 1
THE LIGAND PROPERTIES OF SOME DINITRILES
39
References.
I.
M.S. GILL,
H.S. AHUJA and G.S. RAO, I n o r g .
2.
O.M. BARNHART, C.N. CAUGHLAN and MAZHAN UL-HAQUE, I n o r g .
3.
S.C. JAIN and R. RIVEST, Can. J . Chem. 41,
2130 (1963)
4.
J.L.
Chem. A c t a 4,
5.
MASAKO SUZUKI and TAKEHIKO SHIMANONCHI, Bull. Chem. Soc. Japan 41, 2353 (1968)
6.
Y. KINOSHITA, I .
7.
W.L. DRIESSEN and W.L. GROENEVELD, Rec, T r a y . Chim. 88,
8.
C. SCHWARZENBACH, Die K o m p i e x o m e t r i s c h e T i t r a t i o n , F. Enke V e r l a g , S t u t t g a r t 1965
9.
K.F.
BURMEISTER and M.Y. AL-JANABI,
Inorg.
Chim. Acta 7, 359 (1973)
MATSUBANA and Y.SAITO, B u l l .
PURCELL, J. Am. Chem. Soc. 89,
101
J. REEDIJK, P . W . N . M . v .
11.
J,
12.
A.P.
13.
C.D. JANSEN-LIGTHELM,
Chem. 7, 1135 (1~68)
581 (1970)
Chem. Soc. Japan 32, 741 [1959) 491 [1969)
247 (1967)
LEEUWEN and W.L. GROENEVELD, Rec. T r e y . Chim. 67, 129 (1968)
REEDIJK, W.L. DRIESSEN and W.L. GROENEVELD, Rec. T r a y . Chim. 88, 1095 (1969) ZUUR, A . H . L .
REINTJES and W.L. GROENEVELD, Rec. T r a y . Chim. 89, 385 (1970) W.L. GROENEVELU and J. REEDIJK, Part XV, I n o r g . Chim. A c t a 7, 113 (1973)