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Heteropolynuclear complexes containing oxovanadium(IV) and copper(II)
IHORG.
NUCL.
CHEM.
LETTERS
Vol. 5, PP. 815418,
1969.
Peegamm P~eo.
PtlntNpd in
Gumt Ik'lteln.
HETEROBOLYNUCLEAR COMPLEXES CONTAINING OXOVA~ADI~IV) AND COFTE~II) J . S e l b i n and L. GanEuly Coates Chemical L a b o r a t o r i e S , L o ~ t s i a n a S t a t e U n i v e r s i t y Baton Rouge, L o u i s i a n a 70803 (Reeefved 13 June 1NP)
Introduction We have r e c e n t l y been a t t e m p t i n g t o p r e p a r e h e t e r o p o l y n u c l e a r complexes o f VOe+, a d 1 e l e c t r o n i c system, w i t h o t h e r c e n t r a l m e t a l i o n s , e s p e c i a l l y t h e d 9 Cu~+, b u t a l l p r e v i o u s e f f o r t s have l e d t o o t h e r p r o d u c t s and o t h e r problems ( 1 - 3 ) . We wish now t o r e p o r t t h e f i r s t complexes o f VO2+.
s u c c e s s f u l p r e p a r a t i o n o f such h e t e r o p o l y n u c l e a r
Some o f t h e s e a r e t h e f i r s t
compounds t o c ¢ ~ t a i n a d 1 e l e c -
t r o n i c system c o u p l e d i n t r a m o l e c u l a r l y w i t h a d 9 system, Others r e p r e s e n t the first
examples o f a d 1 system so c o u p l e d t o a d ~° system. R e c e n t l y a nember of d i - and t r i n u c l e a r
which employ c e r t a i n m e t a l t e t r a d e n t a ~ e S c h i f f ' s
complexes were p r e p a r e d ( 4 - 7 ) base complexes ( I ) ( l a b e l e d
MTSB) as l i g a n d s toward a v a r i e t y of s i m i l a r o r d i s s i m i l a r ,
diamagnetic or
paremaEnetic m e t a l i o n s to produce complexes o f t h e t y p e s I I and I I I .
M has
been Cue+ , Ni ~+, o r Zn2+ and MS h a s been Cu2+ o r Zn2+ ( a s h a l i d e s ) or Cu~c, Ni 2+,
Co2+, Fe2+, Mna+, A13+, Mg2+, Ca2+, Sr e+, Ba2+, N+ , and many of the complexes are hydrated.
Zna+ o r Ag+ (as perchlorates);
We have now prepared complexes of types
II and Ill, where M = VO a+, M S = Cu e+ or Zn e+, R = H, K' = ~ C H a ~ e and X = CI" or Br'.
(The llgand is abbreviated ES.)
The specific compounds for which we now have
satisfactory elemental analyses are listed in Table l, along with some analogous Cue+ complexes which were recently reported (5,7).
The colors, magnetic moments,
average esr g values and some pertinent IR bands are also tabulated.
Complete
IR data as well as the more interesting esr and 77OK optlcal spectral data will be published later.
Suffice it to say here that these data firmly support the
heteropolynuclear nature of the new products as does the data in Table i, which 81S
Ill
HETEROPOLYNUCLEAR COMPLEXES
Yol. 5, N.. 10
R..
"~" N / M % -
%- I~1
z
rr
(MTSB)
(MTSB) M" X.
w i l l be d i s c u s s e d b r i e f l y later,
below.
M" (CL04) =
"~O/--'~X
m M'(MTSB}e (CL04) e
Preparation details
w i l l a l s o be p u b l i s h e d
b u t t h e g e n e r a l p r o c e d u r e s w l l l be o u t l i n e d h e r e . Preparative Methods V~ES).CHzOH was prepared from the prevlously syntl~esized tetradentate
ligand H2ES, by reaction of the ligand dissolved in ~MF (dimethylformamlde)
with
VOSO4-SH20 dissolved in DMF in a nitrogen atmosphere under prolonged reflux condltlons.
The compound is stable in an air oven st ii0 ° for many days.
The
methanol could be removed in a nitrogen a~nosphere, as found by TGA (thermogravimetric analysis), at 3700|
Decomposition in nitrogen does not occur until
~ 4 0 0 °.
The heterodlnuclear complex, VO(ES)CuCI2.H20, was prepared by the reaction of V~ES)'CHzOH
in chloroform with anhydrous CuCl2 in ethanol.
The water mole-
cule 8ould be removed in a nitrogen atmosphere, as found by TGA, at 1500.
The
analogous, hut anhydrous, bromide compound was prepared in a similar way. The heterotrlnuclear
complex, CuEV~ES)32 (CI04)2, was prepared by the
reaction of Cu(CIO4)2-xH20 in ethanol with VO(ES).CHzOH in chloroform under reflux conditions.
This compound explodes on41eatlng at about 2200.
compound, VO(Eg)ZnCI2, was prepared in a similar manner.
The zinc
Vol. 5, No. IO
HETEROPOLYNUCLEAR COMPLEXES
117
TABLE Heteropolynuclear Complexes (a) M.P. or Compound
Color
~eff (b)
(e)
Decompn.
Pertinent IR
Bands! ~m "l
Temp. ~°C C-O
C-N
V-O
HeES
yellow
............
124, 280d
15OO
1615
---
V~ES)-CHsOH
dark green
1.95 1.72
e.OO12
270
1535
1625
985
V~ES)CuCIe-HRO
green black
1.90 (c)
2.0960
i~
1550
1620
985
V~ES)CuBre
black
1.69 (c)
2.086~
170
1555
1620
985
220d
1550
1638
989
1625
i010
2.1329 Cu[V~ES)]~CIO4)e
brown
3.93 (c)
e.1991
e. 5061 V ~ ES) ZnCl a
shiny gray
1.91 (c'd)
e. O685
3POd
1560
[Cu(ES) ]e
green
1.84 (d)
---(g)
....
1532(f) 1630
---
"Cu(ES) CuCl 2
black
1.48 (d)
---(g)
....
1552(f) 163e
---
Cu(ES) ZnCl 2
red
i. 83 ( c, d)
.-.(g)
....
1551 (f) _(g)
_-_
Cu[Cu(ES)]R(CIO4)a.3HaO
red
1.73 (d)
---(g)
....
1547 (f) -(g)
---
1556 (a) (b) (c) (d)
(e) (f) (g)
ES = N,N'-ethylenebis(salicylldenelmine) dianion. The last four compounds were prepared previously (5,7) and the data cited here for comparison purposes is from that laboratory (7). Room temperature, corrected Gouy values, except for the lower value for V~ES).MeOH, which was obtained in CHCIs by the NMRmethod. Per complex molecule. Per vanadium (or copper) atom. When there is but one paramagnetic metal ion in a complex, the ~ v a l u e ~ r complex and per paramagnetic metal are identical. For example, when VO =" and Zne+ are present both (c) and (d) are applicable. Powdered samples at room temperature. The somewhat complex esr spectra will be reported in detail later. Our assignments from the data of others (?). Not observed or not reported. Discussion Briefly, the evidence for heteropolynuclear complexes is obtained from
the magnetic and IR data of Table 1.
The reduced magnetic moments in dur com-
818
HETEROPOLYNUCLEAR COMPLEXES
Yol..q, No. I0
pounds VO(ES)CuCle-H~O (1.90 B.M. per complex molecule) and VO(ES)CuBr2 (1.69 B.M. per complex molecule) are evidence (but not proof) of strong antiferremagnetic interactions between the d I V0 a+ and the d s Cu e+ , similar to what has been observed (7) in all analogous heterodinuclear species containing two paramaEnetic ions.
However, temperature-dependent magnetic studies have yet to be made by us.
The value of 3.93 B.M. for Cu[V~ES)]~CI04) e implies n_.oantiferremagnetic inter -• actions, which appears strange to us, but which was also found (7) to be the case
for cu[Cu(~S)]2(Cl0~)2.3~0 (where 1.73 B.M. per C.e+ was observed). Looking next at the IR data, we find that the i~00 em-i band of the ligand, presumed to be the C-0 stretching frequency (7-8), increases to 153~ cm -I when the oxygens are bound to one metal atom and increases still further,
to i~50-
60 em-i when the oxygens are bound to two metal atoms, as they would be in the heteropolynuclear structures.
Although this frequency for the C-O stretch has yet
to be confirmed (e.g., with 180 data), the pronounced shift in this frequency is nevertheless diagnostic of the formation of di- and trinuclear complexes. References I.
C. Heitner-Wirguln and J. Selbin, J. Inors. Nucl. Chem., ~
2.
C. Heitner-Wirguin and J. Selbin, Israel J. Chem., ~, 27 (1969).
3.
O. Piovesana and J. Selbin, J. Inor~: Nucl. Chem., in press.
4.
S.J. Gruber, C.M. Harris, and E. Sinn, Inor~. Nucl. Chem. Letters, ~, 495.
5.
S.J. Gruber, C.M. Harris, and E. Sinn, Inor~. Chem., ~, 268 (1968).
6.
3181 (1968).
S.J. Gruber, C.M. Harris, and E. Sinn, Inorg. Nucl. Chem. Letters, !' 107
(1%8) 7.
S.J. Gruber, C.M. Harris, and E. Sinn, J. Inorg. Nucl. Chem., ~ ,
8.
C.M. Harris and E. Sinn, J. Inorg. Nucl. Chem., ~
~23
(1968).
1805 (1968).
NUCL.
CHEM.
LETTERS
Vol. 5, PP. 815418,
1969.
Peegamm P~eo.
PtlntNpd in
Gumt Ik'lteln.
HETEROBOLYNUCLEAR COMPLEXES CONTAINING OXOVA~ADI~IV) AND COFTE~II) J . S e l b i n and L. GanEuly Coates Chemical L a b o r a t o r i e S , L o ~ t s i a n a S t a t e U n i v e r s i t y Baton Rouge, L o u i s i a n a 70803 (Reeefved 13 June 1NP)
Introduction We have r e c e n t l y been a t t e m p t i n g t o p r e p a r e h e t e r o p o l y n u c l e a r complexes o f VOe+, a d 1 e l e c t r o n i c system, w i t h o t h e r c e n t r a l m e t a l i o n s , e s p e c i a l l y t h e d 9 Cu~+, b u t a l l p r e v i o u s e f f o r t s have l e d t o o t h e r p r o d u c t s and o t h e r problems ( 1 - 3 ) . We wish now t o r e p o r t t h e f i r s t complexes o f VO2+.
s u c c e s s f u l p r e p a r a t i o n o f such h e t e r o p o l y n u c l e a r
Some o f t h e s e a r e t h e f i r s t
compounds t o c ¢ ~ t a i n a d 1 e l e c -
t r o n i c system c o u p l e d i n t r a m o l e c u l a r l y w i t h a d 9 system, Others r e p r e s e n t the first
examples o f a d 1 system so c o u p l e d t o a d ~° system. R e c e n t l y a nember of d i - and t r i n u c l e a r
which employ c e r t a i n m e t a l t e t r a d e n t a ~ e S c h i f f ' s
complexes were p r e p a r e d ( 4 - 7 ) base complexes ( I ) ( l a b e l e d
MTSB) as l i g a n d s toward a v a r i e t y of s i m i l a r o r d i s s i m i l a r ,
diamagnetic or
paremaEnetic m e t a l i o n s to produce complexes o f t h e t y p e s I I and I I I .
M has
been Cue+ , Ni ~+, o r Zn2+ and MS h a s been Cu2+ o r Zn2+ ( a s h a l i d e s ) or Cu~c, Ni 2+,
Co2+, Fe2+, Mna+, A13+, Mg2+, Ca2+, Sr e+, Ba2+, N+ , and many of the complexes are hydrated.
Zna+ o r Ag+ (as perchlorates);
We have now prepared complexes of types
II and Ill, where M = VO a+, M S = Cu e+ or Zn e+, R = H, K' = ~ C H a ~ e and X = CI" or Br'.
(The llgand is abbreviated ES.)
The specific compounds for which we now have
satisfactory elemental analyses are listed in Table l, along with some analogous Cue+ complexes which were recently reported (5,7).
The colors, magnetic moments,
average esr g values and some pertinent IR bands are also tabulated.
Complete
IR data as well as the more interesting esr and 77OK optlcal spectral data will be published later.
Suffice it to say here that these data firmly support the
heteropolynuclear nature of the new products as does the data in Table i, which 81S
Ill
HETEROPOLYNUCLEAR COMPLEXES
Yol. 5, N.. 10
R..
"~" N / M % -
%- I~1
z
rr
(MTSB)
(MTSB) M" X.
w i l l be d i s c u s s e d b r i e f l y later,
below.
M" (CL04) =
"~O/--'~X
m M'(MTSB}e (CL04) e
Preparation details
w i l l a l s o be p u b l i s h e d
b u t t h e g e n e r a l p r o c e d u r e s w l l l be o u t l i n e d h e r e . Preparative Methods V~ES).CHzOH was prepared from the prevlously syntl~esized tetradentate
ligand H2ES, by reaction of the ligand dissolved in ~MF (dimethylformamlde)
with
VOSO4-SH20 dissolved in DMF in a nitrogen atmosphere under prolonged reflux condltlons.
The compound is stable in an air oven st ii0 ° for many days.
The
methanol could be removed in a nitrogen a~nosphere, as found by TGA (thermogravimetric analysis), at 3700|
Decomposition in nitrogen does not occur until
~ 4 0 0 °.
The heterodlnuclear complex, VO(ES)CuCI2.H20, was prepared by the reaction of V~ES)'CHzOH
in chloroform with anhydrous CuCl2 in ethanol.
The water mole-
cule 8ould be removed in a nitrogen atmosphere, as found by TGA, at 1500.
The
analogous, hut anhydrous, bromide compound was prepared in a similar way. The heterotrlnuclear
complex, CuEV~ES)32 (CI04)2, was prepared by the
reaction of Cu(CIO4)2-xH20 in ethanol with VO(ES).CHzOH in chloroform under reflux conditions.
This compound explodes on41eatlng at about 2200.
compound, VO(Eg)ZnCI2, was prepared in a similar manner.
The zinc
Vol. 5, No. IO
HETEROPOLYNUCLEAR COMPLEXES
117
TABLE Heteropolynuclear Complexes (a) M.P. or Compound
Color
~eff (b)
Decompn.
Pertinent IR
Bands! ~m "l
Temp. ~°C C-O
C-N
V-O
HeES
yellow
............
124, 280d
15OO
1615
---
V~ES)-CHsOH
dark green
1.95 1.72
e.OO12
270
1535
1625
985
V~ES)CuCIe-HRO
green black
1.90 (c)
2.0960
i~
1550
1620
985
V~ES)CuBre
black
1.69 (c)
2.086~
170
1555
1620
985
220d
1550
1638
989
1625
i010
2.1329 Cu[V~ES)]~CIO4)e
brown
3.93 (c)
e.1991
e. 5061 V ~ ES) ZnCl a
shiny gray
1.91 (c'd)
e. O685
3POd
1560
[Cu(ES) ]e
green
1.84 (d)
---(g)
....
1532(f) 1630
---
"Cu(ES) CuCl 2
black
1.48 (d)
---(g)
....
1552(f) 163e
---
Cu(ES) ZnCl 2
red
i. 83 ( c, d)
.-.(g)
....
1551 (f) _(g)
_-_
Cu[Cu(ES)]R(CIO4)a.3HaO
red
1.73 (d)
---(g)
....
1547 (f) -(g)
---
1556 (a) (b) (c) (d)
(e) (f) (g)
ES = N,N'-ethylenebis(salicylldenelmine) dianion. The last four compounds were prepared previously (5,7) and the data cited here for comparison purposes is from that laboratory (7). Room temperature, corrected Gouy values, except for the lower value for V~ES).MeOH, which was obtained in CHCIs by the NMRmethod. Per complex molecule. Per vanadium (or copper) atom. When there is but one paramagnetic metal ion in a complex, the ~ v a l u e ~ r complex and per paramagnetic metal are identical. For example, when VO =" and Zne+ are present both (c) and (d) are applicable. Powdered samples at room temperature. The somewhat complex esr spectra will be reported in detail later. Our assignments from the data of others (?). Not observed or not reported. Discussion Briefly, the evidence for heteropolynuclear complexes is obtained from
the magnetic and IR data of Table 1.
The reduced magnetic moments in dur com-
818
HETEROPOLYNUCLEAR COMPLEXES
Yol..q, No. I0
pounds VO(ES)CuCle-H~O (1.90 B.M. per complex molecule) and VO(ES)CuBr2 (1.69 B.M. per complex molecule) are evidence (but not proof) of strong antiferremagnetic interactions between the d I V0 a+ and the d s Cu e+ , similar to what has been observed (7) in all analogous heterodinuclear species containing two paramaEnetic ions.
However, temperature-dependent magnetic studies have yet to be made by us.
The value of 3.93 B.M. for Cu[V~ES)]~CI04) e implies n_.oantiferremagnetic inter -• actions, which appears strange to us, but which was also found (7) to be the case
for cu[Cu(~S)]2(Cl0~)2.3~0 (where 1.73 B.M. per C.e+ was observed). Looking next at the IR data, we find that the i~00 em-i band of the ligand, presumed to be the C-0 stretching frequency (7-8), increases to 153~ cm -I when the oxygens are bound to one metal atom and increases still further,
to i~50-
60 em-i when the oxygens are bound to two metal atoms, as they would be in the heteropolynuclear structures.
Although this frequency for the C-O stretch has yet
to be confirmed (e.g., with 180 data), the pronounced shift in this frequency is nevertheless diagnostic of the formation of di- and trinuclear complexes. References I.
C. Heitner-Wirguln and J. Selbin, J. Inors. Nucl. Chem., ~
2.
C. Heitner-Wirguin and J. Selbin, Israel J. Chem., ~, 27 (1969).
3.
O. Piovesana and J. Selbin, J. Inor~: Nucl. Chem., in press.
4.
S.J. Gruber, C.M. Harris, and E. Sinn, Inor~. Nucl. Chem. Letters, ~, 495.
5.
S.J. Gruber, C.M. Harris, and E. Sinn, Inor~. Chem., ~, 268 (1968).
6.
3181 (1968).
S.J. Gruber, C.M. Harris, and E. Sinn, Inorg. Nucl. Chem. Letters, !' 107
(1%8) 7.
S.J. Gruber, C.M. Harris, and E. Sinn, J. Inorg. Nucl. Chem., ~ ,
8.
C.M. Harris and E. Sinn, J. Inorg. Nucl. Chem., ~
~23
(1968).
1805 (1968).