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Complexes with sulfur and selenium donors—II. Preparation and properties of 0,0′-dimethyldithiophosphate complexes
INORG.
NUCL.
CHEM.
LETTERS
Vol. 6, pp.
475-478,
1970.
Pergamon
Press.
COMPLEXES WITH SULFUR AND SELENIUM DONORS--II.
Printed
in
Great
Britain
PREPARATION
AND PROPERTIES OF O,O'-DIMETHYLDITHIOPHOSPHATE COMPLEXES I Gerald M. Woltermann and John R. Wasson Department of Chemistry, University of Kentucky Lexington, Kentucky 40506 (Received 25 F e b r ~
1970; ~ v i s e d 19 March 1970)
Metal complexes of 0,O',dlalkyldithlophosphoric acids have been known for many years (2). The
most
extensively investigated complexes have been
those of 0,0'-dlethyldlthiophosphoric acid which have a variety of applications in analytical methods.
Recent structural work (3) and interest in
metal-sulfur bonding (4) has prompted us to report our studies on 0,0'dimethyldlthiophosphate (Me-dtp) complexes. Experimental O,0'-Dimeth~idithiophosphoric Acid.
A stolchiometrlc amount of absolute
methanol was added to phosphorus(V) sulfide and mixture stirred magnetically until it became clear (about one hour).
The acid obtained (5) from the
methanolysls of phosphorus(V) sulfide was used immediately for the preparation of the metal complexes.
Before the acid can be stored it is
necessary to bubble nitrogen gas through it for several minutes. Complexes.
Except for the indium compound, the complexes were obtained
by stirring a mixture of an excess of metal salt with the acid for an hour and then extracting with chloroform.
The metal salts employed were nickel(II)
chloride hexahydrate, zinc carbonate, cadmium nitrate, and lead nitrate. The complexes were recrystalllzed several times from chloroform.
The cadmium
and lead compounds were recrystallized from a ho~ ethanol-acetone (i:I) mixture. In(Me-dtp) 3
was precipitated from a dilute nitric acid solution of indlum(III)
475
476
C O M P L E X E S WITH S U L F U R AND S E L E N I U M D O N O R S - I I .
nitrate.
Vol. 6, No.
The white precipitate was isolated by filtration and recrystalllzed
from chloroform. orange crystals,
Ni(Me-dtp) 2 and Pd(Me-dtp) 2 were obtained as purple and respectively,
while the other complexes were isolated as
white solids. Proton nuclear magnetic resonance spectra at ambient temperatures saturated solutions of the complexes
in d e u t e r o c h l o r o f o r m w e r e
Varian HA-60-1L and T-60 spectrometers.
Tetramethylsilane
of
obtained with
was employed as
an internal standard.
TABLE I Analytical Data Compound
%Carbon Calcd. Found
% Hydrogen Calcd. Found
Melting Point, °C
Ni(Me-dtp) 2
12.88
12.79
3.46
3.38
132-134
Pd(Me-dtp) 2
11.42
11.43
3.07
Zn(Me-dtp) 2
12.65
12.41
3.40
3.28
dec. 230
Cd(Me-dtp) 2
11.26
Ii.i0
3.02
~2.88
174-176
Pb(Me-dtp) 2
9.21
8.92
2.47
2.20
145-147
In(Me-dtp) 3
12.29
11.98
3.09
3.14
150-152
Results and Discussion The pmr spectra of Me-dtp complexes are reported in Table II. spectra exhibit a doublet structure
from 31p splitting of the methyl peak.
Although it is likely that the zinc and cadmium complexes
are polymeric in
the solid state (3), the pmr spectra are indicative of a bls-chelate in solution. of association
The
Molecular weight studies
(4) are indicative
structure
of a small amount
of the zinc complex in chloroform solution but this does not
have any effect on the pmr spectra.
The spectra of dilute solutions were
identical to those reported in Table II. The pmr spectra and ready solubility
in a variety of organic solvents
5
Vol 6. N o 5
COMPLEXES WITH S U L F U R AND SELENIUM DONORS-II.
477
TABLE II Proton Magnetic Resonance Data Compound
Chemical S h i f t , ~
JPOCB3, cps
(CH30)3P=O
6.23
ii.0
Ni(Me-dtp) 2
6 08
15.6
Pd(Me-dtp) 2
6 17
15.6
Zn(Me-dtp) 2
6 20
15.8
a(6 19)
(16)
Cd(Me-dtp) 2
6 15
15.7
Pb(Me-dtp) 2
6 23
16.0
In(Me-dtp) 3
6 03
15.6
Tl(Me-dtp) a
6 33
14
a) Reference 4.
are consistent with monomeric bis-chelate structures which can be proposed for the complexes.
The diamagnetism and electronic spectra of the nickel(II)
and palladium(ll) complexes indicate planar structures (6). The zinc, cadmium, and lead compounds are probably tetrahedral and the indium complex has octahedral geometry.
In view of the variety of coordination geometries and
metal ions it is rather surprising that the chemical shifts and POCH 3 coupling constants are so similar and not greatly ~ifferent from trimethylphosphate.
This implies that transmission of metal d orbital effects via
sulfur and phosphorus outer d orbitals (7) is negligible and that the orbital hybridization employed by phosphorus is essentially constant.
Acknowledgment This work was partially supported by the University of Kentucky Researc~ Foundation.
478
COMPLEXES WITH SULFUR AND SELENIUM DONORS-II.
Vol. 6, No. 5
References 1.
Part I: J. R. Wasson, S. J. Wasson, and G. W. Woltermann, Inorg. Chem., 9, (1970), in press.
2.
D. E. Goldberg, W. C. Fernellus, and M. Shamma, Inorg. Syn., 6, 142 (1960).
3.
S. L. Lawton and G. T. Kokotailo, Inor$. Chem., 8, 2410 (1969).
4.
F. Bonatl and G. Minghettl, Inor~. Chem. Acta, ~, 161 (1969).
5.
T. W. Mastin, G. R. Norman and E. A. Weilmuenster, J. Amer. Chem. Soc., 67, 1662 (1945).
6.
G.. M. Woltermann and J. R. Wasson, unpublished results. The corresponding ethyl derivatives have been described by C. K. Jorgensen, J. Inorgz Nucl. Chem., 24, 1571 (1962).
7.
D. S. Urch, J. Chem. Soc. (A), 3026 (1969); E. A. C. Lucken, Structure and Bonding 6, i (1969).
NUCL.
CHEM.
LETTERS
Vol. 6, pp.
475-478,
1970.
Pergamon
Press.
COMPLEXES WITH SULFUR AND SELENIUM DONORS--II.
Printed
in
Great
Britain
PREPARATION
AND PROPERTIES OF O,O'-DIMETHYLDITHIOPHOSPHATE COMPLEXES I Gerald M. Woltermann and John R. Wasson Department of Chemistry, University of Kentucky Lexington, Kentucky 40506 (Received 25 F e b r ~
1970; ~ v i s e d 19 March 1970)
Metal complexes of 0,O',dlalkyldithlophosphoric acids have been known for many years (2). The
most
extensively investigated complexes have been
those of 0,0'-dlethyldlthiophosphoric acid which have a variety of applications in analytical methods.
Recent structural work (3) and interest in
metal-sulfur bonding (4) has prompted us to report our studies on 0,0'dimethyldlthiophosphate (Me-dtp) complexes. Experimental O,0'-Dimeth~idithiophosphoric Acid.
A stolchiometrlc amount of absolute
methanol was added to phosphorus(V) sulfide and mixture stirred magnetically until it became clear (about one hour).
The acid obtained (5) from the
methanolysls of phosphorus(V) sulfide was used immediately for the preparation of the metal complexes.
Before the acid can be stored it is
necessary to bubble nitrogen gas through it for several minutes. Complexes.
Except for the indium compound, the complexes were obtained
by stirring a mixture of an excess of metal salt with the acid for an hour and then extracting with chloroform.
The metal salts employed were nickel(II)
chloride hexahydrate, zinc carbonate, cadmium nitrate, and lead nitrate. The complexes were recrystalllzed several times from chloroform.
The cadmium
and lead compounds were recrystallized from a ho~ ethanol-acetone (i:I) mixture. In(Me-dtp) 3
was precipitated from a dilute nitric acid solution of indlum(III)
475
476
C O M P L E X E S WITH S U L F U R AND S E L E N I U M D O N O R S - I I .
nitrate.
Vol. 6, No.
The white precipitate was isolated by filtration and recrystalllzed
from chloroform. orange crystals,
Ni(Me-dtp) 2 and Pd(Me-dtp) 2 were obtained as purple and respectively,
while the other complexes were isolated as
white solids. Proton nuclear magnetic resonance spectra at ambient temperatures saturated solutions of the complexes
in d e u t e r o c h l o r o f o r m w e r e
Varian HA-60-1L and T-60 spectrometers.
Tetramethylsilane
of
obtained with
was employed as
an internal standard.
TABLE I Analytical Data Compound
%Carbon Calcd. Found
% Hydrogen Calcd. Found
Melting Point, °C
Ni(Me-dtp) 2
12.88
12.79
3.46
3.38
132-134
Pd(Me-dtp) 2
11.42
11.43
3.07
Zn(Me-dtp) 2
12.65
12.41
3.40
3.28
dec. 230
Cd(Me-dtp) 2
11.26
Ii.i0
3.02
~2.88
174-176
Pb(Me-dtp) 2
9.21
8.92
2.47
2.20
145-147
In(Me-dtp) 3
12.29
11.98
3.09
3.14
150-152
Results and Discussion The pmr spectra of Me-dtp complexes are reported in Table II. spectra exhibit a doublet structure
from 31p splitting of the methyl peak.
Although it is likely that the zinc and cadmium complexes
are polymeric in
the solid state (3), the pmr spectra are indicative of a bls-chelate in solution. of association
The
Molecular weight studies
(4) are indicative
structure
of a small amount
of the zinc complex in chloroform solution but this does not
have any effect on the pmr spectra.
The spectra of dilute solutions were
identical to those reported in Table II. The pmr spectra and ready solubility
in a variety of organic solvents
5
Vol 6. N o 5
COMPLEXES WITH S U L F U R AND SELENIUM DONORS-II.
477
TABLE II Proton Magnetic Resonance Data Compound
Chemical S h i f t , ~
JPOCB3, cps
(CH30)3P=O
6.23
ii.0
Ni(Me-dtp) 2
6 08
15.6
Pd(Me-dtp) 2
6 17
15.6
Zn(Me-dtp) 2
6 20
15.8
a(6 19)
(16)
Cd(Me-dtp) 2
6 15
15.7
Pb(Me-dtp) 2
6 23
16.0
In(Me-dtp) 3
6 03
15.6
Tl(Me-dtp) a
6 33
14
a) Reference 4.
are consistent with monomeric bis-chelate structures which can be proposed for the complexes.
The diamagnetism and electronic spectra of the nickel(II)
and palladium(ll) complexes indicate planar structures (6). The zinc, cadmium, and lead compounds are probably tetrahedral and the indium complex has octahedral geometry.
In view of the variety of coordination geometries and
metal ions it is rather surprising that the chemical shifts and POCH 3 coupling constants are so similar and not greatly ~ifferent from trimethylphosphate.
This implies that transmission of metal d orbital effects via
sulfur and phosphorus outer d orbitals (7) is negligible and that the orbital hybridization employed by phosphorus is essentially constant.
Acknowledgment This work was partially supported by the University of Kentucky Researc~ Foundation.
478
COMPLEXES WITH SULFUR AND SELENIUM DONORS-II.
Vol. 6, No. 5
References 1.
Part I: J. R. Wasson, S. J. Wasson, and G. W. Woltermann, Inorg. Chem., 9, (1970), in press.
2.
D. E. Goldberg, W. C. Fernellus, and M. Shamma, Inorg. Syn., 6, 142 (1960).
3.
S. L. Lawton and G. T. Kokotailo, Inor$. Chem., 8, 2410 (1969).
4.
F. Bonatl and G. Minghettl, Inor~. Chem. Acta, ~, 161 (1969).
5.
T. W. Mastin, G. R. Norman and E. A. Weilmuenster, J. Amer. Chem. Soc., 67, 1662 (1945).
6.
G.. M. Woltermann and J. R. Wasson, unpublished results. The corresponding ethyl derivatives have been described by C. K. Jorgensen, J. Inorgz Nucl. Chem., 24, 1571 (1962).
7.
D. S. Urch, J. Chem. Soc. (A), 3026 (1969); E. A. C. Lucken, Structure and Bonding 6, i (1969).