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Binuclear complexes of silicon(IV) chloride with nickel(II) salicylaldoximates
Po/yhedm Vol. 3, No. 5, pp. 6034% Printed in Great Britain.
0277-5387/84 $3.00 + .OO Q 1984 Pcrgamon Press Ltd.
1984
NOTE BINUCLEAR COMPLEXES OF SILICON(IV) CHLORIDE WITH NICKEL(U) SALICYLALDOXIMATES N. S. BIRADAR, V. L. RODDABABANAGOUDAR and T. M. AMlNABHAVI* Department of Chemistry, Kamatak University, Dharwad 580003, India (Received 13 June 1983; accepted 10 October 1983) Abstract-Some binuclear complexes of silicon(IV) chloride and nickel(I1) salicylaldoximates were synthesized and characterized by elemental analyses, conductivity measurements, magnetic and spectral data. The complexes were proved to be 1: 1 SiCl, adducts. The resulting complexes were amorphous in nature and electrolytes in solution. In recent years there has been a continuing interest in the synthesis and characterization of binuclear, bimetallic complexes.’ In a previous study,’ nickel(I1) aldoximates and tin(IV) chloride were shown to form 1: 1 adducts. In this continuing study bimetallic complexes of nickel(I1) salicyaldoximate and silicon tetrachloride were prepared. The complexes were characterized by elemental analysis, conductivity measurements, magnetic measurements, electronic and IR spectra. EXPERIMENTAL All the chemicals used in this work were of reagent grade and were used without further purification. The substituted salicylaldoximines were prepared by dissolving hydroxylamine hydrochloride (0.1 mole) in the minimum amount of water, then adding this solution to a hot ethanolic solution of the substituted salicylaldehyde (0.1 mole). The mixture was then mixed with nickel(I1) chloride and refluxed for 30 min. Upon cooling, crystals corresponding to nickel(I1) salicylaldoximates were obtained with a yield of 80%. These were washed repeatedly with ethanol, filtered, then dried over anhydrous calcium chloride. The nickel(I1) salicylaldoximates of the type Ni[O(HON CH)C,H,R], were prepared. Where,
Ligand
R
A
H 3-CH, 4-CH 5-CH: S-Cl
B : E
The binuclear complexes were prepared by the reaction of nickel(I1) salicylaldoximates with silicon tetrachloride. Equimolar quantities (0.01 mole) of both nickel(I1) salicylaldoximates and silicon(IV) tetrachloride were taken in 100 cm3 of dry benzene in a 250 cm3 round bottom flask. The reaction mixture was refluxed for 12 hr. The solid precipitate formed was filtered, washed repeatedly with dry benzene and dried under vacuum over P,O,. Approximately 75-80x yields of the complexes were obtained in all reactions. Table 1 correlates each nickel(I1) salicylaldoximate (A-E) with its corresponding SiCl, adduct (I-V). Elemental analyses were carried out by a procedure described elsewhere.3 Gravimetric technique was used to estimate silicon as its oxide and nickel(I1) as its dimethylglyoximate; chloride was determined as silver chloride and nitrogen by micro-Kjeldahl method. Conductivities were measured in dimethylformamide (DMF) using an Elico-CM-82 conductivity bridge with a cell having a cell constant of 0.829 cm - ‘. All conductivity measurements were performed at room temperature using 10m3M solutions of complex. Magnetic susceptibility measurements were made using a Gouy balance. At least three measurements were averaged for each compound at 298 K, the observed susceptibilities
Name Bis(Salicylaldoximato)nickel(II) Bis(3-methylsalicylaldoximato)nickel(II) Bis(4-methylsalicylaldoximato)nickel(II) Bis(S-methylsalicylaldoximato)nickel(II) Bis(Schlorosalicylaldoximato)nickel@)
*Author to whom correspondence should be addressed. 603
Notes
604
Table 1. Physical, spectroscopic and analytical data of complexes Liqand
Bmpirical fomrdla of complex
'xIll(a)
% si(')
% t.P)
% Clta)
MO-&r b-ian2 -1 ill010
A
(C14H1$‘J20,~i)S~1,
11.52 (11.60)
B
(56’3 16Nz”4Ni
)sic14
lo. 76 (10.98)
C
(C16H16N2D4Ni)S~C14
11.03 (10.98)
D
(C16H16N204Ni)S*14
11.30 (10.98)
E
(C16HloN204C12N~)SiC14
9.67 ( 9.78)
5.62 (5.60)
5.41 (5.30)
4.68 (4.72)
(a)
-
values in the psrenthesio are the calculatd
(b)
-
3T13
Ir,CPl
(c)
-
3Tl +
'Al(")
were corrected for diamagnetic contributions4 and cldf was derived assuming the Curie law applied. The JR spectra were obtained using a CarlZeiss UR-10 IR spectrometer. Samples were prepared as KBr pellets. UV-visible spectra were obtained on a Perkin-Elmer, 492-5000 spectrophotometer. RESULTS AND DISCUSSION Analytical
data
All the complexes (I-V) are coloured, amorphous and insoluble in common organic solvents. The complexes were soluble in dimethylformamide (DMF) and dimethylsulphoxide (DMSO). The elemental analyses (see Table 1) indicate a 1: 1 Sic& adduct formation. The molar conductivities are in the range 90-102 D - ’ cm’ mole-’ indicating a 1: 1 electrolytic behaviour. Magnetic properties
For nickel(I1) in a regular tetrahedral field, the ground state is an orbitally degenerate T state and a large orbital contribution is expected giving, pdf in the range 3.5-4.0 B.Me5 In the present study the effective magnetic moments are in the range of 3.4-4.01 B.M. (see Table 1) suggesting a tetrahedral configuration It therefore appears that the nickel stereochemistry has changed from square planar to tetrahedral configuration. Electronic spectra
The ‘spectra of square planar four coordinated nickel(I1) compounds exhibit a consistent medium
Electronic spectral
pe,, B.M.
tranrritione
(b)
(C)
5.46 (5.60)
28.66 (28.40)
87
690
485
3.62
5.23 (5.30)
25.52 (26.89)
92
680
470
3.90
5.29 (5.30)
27.06 (26.89)
78
695
480
4.00
5.33 (5.301
26.77 (26.89)
97
680
465
3.55
4.91 (4.72)
23.88 (23.95)
79
700
480
3.42
nmber8
intensity band at 470 nm which is typical of square planar nickel6 and the presence of no bands above 1000 nm is a further proof of the planarity of the ligand.’ The data presented in Table 1 suggest that the SiCJ adducts reported here are pseudotetrahedral nickel(I1) compounds. The band at 700-650 nm is assigned to 3Tl+3T’(P) transition while a band at 500-450 nm may be assigned to a ‘T,-+‘A,(G) transition or charge transfer. These data taken together with the high values of magnetic moments (3.6-4.0 B.M.) suggest that the complexes are of tetrahedral nature.“pg IR spectra
The important IR frequencies and their assignments are reported in Tables 2 and 3. An intense band at 164&1635 cm-’ observed in the nickel(I1) salicylaldoximate complexes (A-E) is ascribed to the O-H deformation vibration of the oxime moiety. The band is shifted to 1650 cm - ’ on formation of the binuclear complexes (I-V) thus indicating the formation of a SicOH linkage.2 The strong absorption bands in the range 1225-l 185 cm-’ and 925-910 cm - ’ are assigned to v(N-O).‘~~” One of the bands at 9 15 cm - ’ in the spectra of nickel(I1) salicylaldoximates splits when the complexes react with silicon(W) chloride to form binuclear complexes. This evidence corroborates the fact that the oxygen of the oxime moiety bonds to the silicon. This bonding is further confirmed by the presence of a band at 800-780 cm - ’ assigned to v(Si-0).13 The bands observed at 550 cm-’ and 470 cm-’ in the bis-complexes are assigned to v(Ni-N) and
Notes
605
Table 2. IR frequencies (in cm-‘) of nickel(I1) salicylaldoximates and their assignments s.vo.
sssiqrnnentll
L4ands B
A 1
intramolecular bonjedai
2
-cni deformation
hydv
D
2
L
3225br.m
3250br.m
323cbr.w
3225br
3238br.w
16408
1640a
1640a
1640s
16350
3
9t-N)
1605s
1602s
16088
16108
1600s
4
-j(coc) aranatic stretch
1ssoe 15OOB
1575s 15106
1550s 15258
154Oa 15OOS
1540s 1495s
1320s
1325s
1320e
13200
1320s
12108
1225m 915br
1205s 9tobr
11908 915br
ll850 920br
5
Phenolic
6
JW-0)
v(C-0,
92obr
7
$(Wl-N)
5408
53%
55cm
5408
5358
8
3p&O)
47im
46Yn
465m
46%
465111
(II &rom;
br.m. = broad mediunt br.w - broad weak3
Table 3. IR frequencies (in cm-‘) of silicon(N)
br - broad;
m-m&i-
chloride complexes with nickel(H) salicylaldoximates and
their assignments
stretchlw
1
44
2
-OH deformation
3
a -
+(CIN)
stretch
atronat
and ammatic
br.m. =
I
II .rC
III
3433br.w
3340s
33Wx.
1650
1643
1647
1633
1652
16160 16048 149Qn
1620m 1572br.m 1500br.m
16128
16l080 1550s 1soan
1615s 15428 14838
13100
13008
13058
1295s
13100
1215w 92ospl
121ow 9lOw
12lOu 92ospl
122ow 925spl
1215w 915apl
IV s
V 3400br.m
C-C
:EEz
.
8C0a
7858
7908
8008
780s
62aa
61-31~
610~
62~
63(m
54cm
560br.m
54%
56Sm
550br.m
broadm63lumt w+ weak1 opl I splitttidtbr- broad
v(NiL0) respectively. These bands do not shift on formation of the binuclear complexes. A strong band observed around 610-630 cm-’ is assigned to ~(Si-cl).‘~ A medium intensity band observed around 15 10 cm - ’ is ascribed to o-disubstituted benzene ring vibrations. The bands observed at 1610 cm - ’ due to azomethine group in nickel(I1)
salicyalaldoximate have been shifted to 1620 cm - ’ on complexation with silicon(W) tetrachloride; the split in this band is further evidence of the fact that the symmetry around nickel(I1) might have changed. This change in symmetry is further supported by the shift of phenolic v(C-0) stretch from 1325 cm -’ in nickel(I1) salicylaldoximate to
606
Notes
1305 cm-’ in the binuclear complexes. Finally, in of the complexes I-V a shallow broad band at 3400 cm -I is attributed to v(O-H). the spectra
Acknowledgements-We gratefully extend our thanks to the referees for constructive comments on this work.
REFERENCES 1. N. Voiculescu, Rev. Roum. Chim. 1977, 22, 237. 2. N. S. Biradar, B. R. Patil and V. H. Kulkami, J. Inorg. Nucl. Chem. 1975, 37, 1901. 3. A. I. Vogel, Textbook of Quantitative Inorganic Analysis, 3rd Edn. Longmans Green, New York (1969). 4. C. J. O’Connor, Magnetochemistry-advances in theory and htrumentation, In Progress in Inorganic Chemistry (Edited by S. J. Lippard), Vol. 29. Wiley, New York (1982).
5. M. A. Weiner and P. Schwartz, Inorg. Chem. 1975, 14, 1715. 6. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 3rd Edn, Wiley Eastern, New Delhi (1976). 7. A. B. P. Lever, Inorganic Electronic Spectroscopy (Edited by Lappert). Elsevier, Amsterdam (1968). 8. N. S. Gill and R. S. Nyholm, J. Chem. Sot. 1959, 3997. 9. F. A. Cotton and R. Francis, J. Am. Chem. Sot. 1960, 82, 2986. 10. R. Blinc and H. Hadzi, J. Chem. Sot. A, 1958,4536. 11. A. Palm and H. Werbin, Can. J. Chem. 1953, 31, 1004. 12. K. K. Ramaswamy, C. J. Jose and D. N. Sen, Znd. J. Chem. 1967, 5, 156. 13. A. L. Smith, Spectrochim. Acta. 1963, 19, 849.
0277-5387/84 $3.00 + .OO Q 1984 Pcrgamon Press Ltd.
1984
NOTE BINUCLEAR COMPLEXES OF SILICON(IV) CHLORIDE WITH NICKEL(U) SALICYLALDOXIMATES N. S. BIRADAR, V. L. RODDABABANAGOUDAR and T. M. AMlNABHAVI* Department of Chemistry, Kamatak University, Dharwad 580003, India (Received 13 June 1983; accepted 10 October 1983) Abstract-Some binuclear complexes of silicon(IV) chloride and nickel(I1) salicylaldoximates were synthesized and characterized by elemental analyses, conductivity measurements, magnetic and spectral data. The complexes were proved to be 1: 1 SiCl, adducts. The resulting complexes were amorphous in nature and electrolytes in solution. In recent years there has been a continuing interest in the synthesis and characterization of binuclear, bimetallic complexes.’ In a previous study,’ nickel(I1) aldoximates and tin(IV) chloride were shown to form 1: 1 adducts. In this continuing study bimetallic complexes of nickel(I1) salicyaldoximate and silicon tetrachloride were prepared. The complexes were characterized by elemental analysis, conductivity measurements, magnetic measurements, electronic and IR spectra. EXPERIMENTAL All the chemicals used in this work were of reagent grade and were used without further purification. The substituted salicylaldoximines were prepared by dissolving hydroxylamine hydrochloride (0.1 mole) in the minimum amount of water, then adding this solution to a hot ethanolic solution of the substituted salicylaldehyde (0.1 mole). The mixture was then mixed with nickel(I1) chloride and refluxed for 30 min. Upon cooling, crystals corresponding to nickel(I1) salicylaldoximates were obtained with a yield of 80%. These were washed repeatedly with ethanol, filtered, then dried over anhydrous calcium chloride. The nickel(I1) salicylaldoximates of the type Ni[O(HON CH)C,H,R], were prepared. Where,
Ligand
R
A
H 3-CH, 4-CH 5-CH: S-Cl
B : E
The binuclear complexes were prepared by the reaction of nickel(I1) salicylaldoximates with silicon tetrachloride. Equimolar quantities (0.01 mole) of both nickel(I1) salicylaldoximates and silicon(IV) tetrachloride were taken in 100 cm3 of dry benzene in a 250 cm3 round bottom flask. The reaction mixture was refluxed for 12 hr. The solid precipitate formed was filtered, washed repeatedly with dry benzene and dried under vacuum over P,O,. Approximately 75-80x yields of the complexes were obtained in all reactions. Table 1 correlates each nickel(I1) salicylaldoximate (A-E) with its corresponding SiCl, adduct (I-V). Elemental analyses were carried out by a procedure described elsewhere.3 Gravimetric technique was used to estimate silicon as its oxide and nickel(I1) as its dimethylglyoximate; chloride was determined as silver chloride and nitrogen by micro-Kjeldahl method. Conductivities were measured in dimethylformamide (DMF) using an Elico-CM-82 conductivity bridge with a cell having a cell constant of 0.829 cm - ‘. All conductivity measurements were performed at room temperature using 10m3M solutions of complex. Magnetic susceptibility measurements were made using a Gouy balance. At least three measurements were averaged for each compound at 298 K, the observed susceptibilities
Name Bis(Salicylaldoximato)nickel(II) Bis(3-methylsalicylaldoximato)nickel(II) Bis(4-methylsalicylaldoximato)nickel(II) Bis(S-methylsalicylaldoximato)nickel(II) Bis(Schlorosalicylaldoximato)nickel@)
*Author to whom correspondence should be addressed. 603
Notes
604
Table 1. Physical, spectroscopic and analytical data of complexes Liqand
Bmpirical fomrdla of complex
'xIll(a)
% si(')
% t.P)
% Clta)
MO-&r b-ian2 -1 ill010
A
(C14H1$‘J20,~i)S~1,
11.52 (11.60)
B
(56’3 16Nz”4Ni
)sic14
lo. 76 (10.98)
C
(C16H16N2D4Ni)S~C14
11.03 (10.98)
D
(C16H16N204Ni)S*14
11.30 (10.98)
E
(C16HloN204C12N~)SiC14
9.67 ( 9.78)
5.62 (5.60)
5.41 (5.30)
4.68 (4.72)
(a)
-
values in the psrenthesio are the calculatd
(b)
-
3T13
Ir,CPl
(c)
-
3Tl +
'Al(")
were corrected for diamagnetic contributions4 and cldf was derived assuming the Curie law applied. The JR spectra were obtained using a CarlZeiss UR-10 IR spectrometer. Samples were prepared as KBr pellets. UV-visible spectra were obtained on a Perkin-Elmer, 492-5000 spectrophotometer. RESULTS AND DISCUSSION Analytical
data
All the complexes (I-V) are coloured, amorphous and insoluble in common organic solvents. The complexes were soluble in dimethylformamide (DMF) and dimethylsulphoxide (DMSO). The elemental analyses (see Table 1) indicate a 1: 1 Sic& adduct formation. The molar conductivities are in the range 90-102 D - ’ cm’ mole-’ indicating a 1: 1 electrolytic behaviour. Magnetic properties
For nickel(I1) in a regular tetrahedral field, the ground state is an orbitally degenerate T state and a large orbital contribution is expected giving, pdf in the range 3.5-4.0 B.Me5 In the present study the effective magnetic moments are in the range of 3.4-4.01 B.M. (see Table 1) suggesting a tetrahedral configuration It therefore appears that the nickel stereochemistry has changed from square planar to tetrahedral configuration. Electronic spectra
The ‘spectra of square planar four coordinated nickel(I1) compounds exhibit a consistent medium
Electronic spectral
pe,, B.M.
tranrritione
(b)
(C)
5.46 (5.60)
28.66 (28.40)
87
690
485
3.62
5.23 (5.30)
25.52 (26.89)
92
680
470
3.90
5.29 (5.30)
27.06 (26.89)
78
695
480
4.00
5.33 (5.301
26.77 (26.89)
97
680
465
3.55
4.91 (4.72)
23.88 (23.95)
79
700
480
3.42
nmber8
intensity band at 470 nm which is typical of square planar nickel6 and the presence of no bands above 1000 nm is a further proof of the planarity of the ligand.’ The data presented in Table 1 suggest that the SiCJ adducts reported here are pseudotetrahedral nickel(I1) compounds. The band at 700-650 nm is assigned to 3Tl+3T’(P) transition while a band at 500-450 nm may be assigned to a ‘T,-+‘A,(G) transition or charge transfer. These data taken together with the high values of magnetic moments (3.6-4.0 B.M.) suggest that the complexes are of tetrahedral nature.“pg IR spectra
The important IR frequencies and their assignments are reported in Tables 2 and 3. An intense band at 164&1635 cm-’ observed in the nickel(I1) salicylaldoximate complexes (A-E) is ascribed to the O-H deformation vibration of the oxime moiety. The band is shifted to 1650 cm - ’ on formation of the binuclear complexes (I-V) thus indicating the formation of a SicOH linkage.2 The strong absorption bands in the range 1225-l 185 cm-’ and 925-910 cm - ’ are assigned to v(N-O).‘~~” One of the bands at 9 15 cm - ’ in the spectra of nickel(I1) salicylaldoximates splits when the complexes react with silicon(W) chloride to form binuclear complexes. This evidence corroborates the fact that the oxygen of the oxime moiety bonds to the silicon. This bonding is further confirmed by the presence of a band at 800-780 cm - ’ assigned to v(Si-0).13 The bands observed at 550 cm-’ and 470 cm-’ in the bis-complexes are assigned to v(Ni-N) and
Notes
605
Table 2. IR frequencies (in cm-‘) of nickel(I1) salicylaldoximates and their assignments s.vo.
sssiqrnnentll
L4ands B
A 1
intramolecular bonjedai
2
-cni deformation
hydv
D
2
L
3225br.m
3250br.m
323cbr.w
3225br
3238br.w
16408
1640a
1640a
1640s
16350
3
9t-N)
1605s
1602s
16088
16108
1600s
4
-j(coc) aranatic stretch
1ssoe 15OOB
1575s 15106
1550s 15258
154Oa 15OOS
1540s 1495s
1320s
1325s
1320e
13200
1320s
12108
1225m 915br
1205s 9tobr
11908 915br
ll850 920br
5
Phenolic
6
JW-0)
v(C-0,
92obr
7
$(Wl-N)
5408
53%
55cm
5408
5358
8
3p&O)
47im
46Yn
465m
46%
465111
(II &rom;
br.m. = broad mediunt br.w - broad weak3
Table 3. IR frequencies (in cm-‘) of silicon(N)
br - broad;
m-m&i-
chloride complexes with nickel(H) salicylaldoximates and
their assignments
stretchlw
1
44
2
-OH deformation
3
a -
+(CIN)
stretch
atronat
and ammatic
br.m. =
I
II .rC
III
3433br.w
3340s
33Wx.
1650
1643
1647
1633
1652
16160 16048 149Qn
1620m 1572br.m 1500br.m
16128
16l080 1550s 1soan
1615s 15428 14838
13100
13008
13058
1295s
13100
1215w 92ospl
121ow 9lOw
12lOu 92ospl
122ow 925spl
1215w 915apl
IV s
V 3400br.m
C-C
:EEz
.
8C0a
7858
7908
8008
780s
62aa
61-31~
610~
62~
63(m
54cm
560br.m
54%
56Sm
550br.m
broadm63lumt w+ weak1 opl I splitttidtbr- broad
v(NiL0) respectively. These bands do not shift on formation of the binuclear complexes. A strong band observed around 610-630 cm-’ is assigned to ~(Si-cl).‘~ A medium intensity band observed around 15 10 cm - ’ is ascribed to o-disubstituted benzene ring vibrations. The bands observed at 1610 cm - ’ due to azomethine group in nickel(I1)
salicyalaldoximate have been shifted to 1620 cm - ’ on complexation with silicon(W) tetrachloride; the split in this band is further evidence of the fact that the symmetry around nickel(I1) might have changed. This change in symmetry is further supported by the shift of phenolic v(C-0) stretch from 1325 cm -’ in nickel(I1) salicylaldoximate to
606
Notes
1305 cm-’ in the binuclear complexes. Finally, in of the complexes I-V a shallow broad band at 3400 cm -I is attributed to v(O-H). the spectra
Acknowledgements-We gratefully extend our thanks to the referees for constructive comments on this work.
REFERENCES 1. N. Voiculescu, Rev. Roum. Chim. 1977, 22, 237. 2. N. S. Biradar, B. R. Patil and V. H. Kulkami, J. Inorg. Nucl. Chem. 1975, 37, 1901. 3. A. I. Vogel, Textbook of Quantitative Inorganic Analysis, 3rd Edn. Longmans Green, New York (1969). 4. C. J. O’Connor, Magnetochemistry-advances in theory and htrumentation, In Progress in Inorganic Chemistry (Edited by S. J. Lippard), Vol. 29. Wiley, New York (1982).
5. M. A. Weiner and P. Schwartz, Inorg. Chem. 1975, 14, 1715. 6. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 3rd Edn, Wiley Eastern, New Delhi (1976). 7. A. B. P. Lever, Inorganic Electronic Spectroscopy (Edited by Lappert). Elsevier, Amsterdam (1968). 8. N. S. Gill and R. S. Nyholm, J. Chem. Sot. 1959, 3997. 9. F. A. Cotton and R. Francis, J. Am. Chem. Sot. 1960, 82, 2986. 10. R. Blinc and H. Hadzi, J. Chem. Sot. A, 1958,4536. 11. A. Palm and H. Werbin, Can. J. Chem. 1953, 31, 1004. 12. K. K. Ramaswamy, C. J. Jose and D. N. Sen, Znd. J. Chem. 1967, 5, 156. 13. A. L. Smith, Spectrochim. Acta. 1963, 19, 849.