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Alkyl- and aryl-platinum(II) complexes from K2[PtCl4] and tetraorganotin compounds in dimethylsulphoxide. Preparation and reactions of complexes [PtR2(DMSO)2] and [PtR(C) (DMSO)2]
Cl8 Journal of Organometallic Chemistry, 170 (1979) ClS-C20 o Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands
Preliminary communication
ALKYL- AND ARYL-PLATINUM(H) COMPLEXES FROM K2 [PtCL] AND TETRAORGANOTIN COMPOUNDS IN DIMETHYLSULPHOXIDE. PREPARATION AND REACTIONS OF COMPLEXES [PtR*(DMSO)* ] AND EPtR(C) (DMSO),I ’
COLIN EABORN*,
KALIPADA
School of Molecular Sciezces,
KUNDU
and ALAN PIDCOCK*
University of Sussex, Brighton BhrI 9QJ (Great Britain)
(Received February 14th, 1979)
Summary The reaction between Kz [PtCl,] and a variety of tetraorganotin compounds SnMe3R (R = Me, aryl) in DMSO gives the complexes cis-[PtR,(DMSO),] and in which the DMSO ligands are bound to Pt through S trans-[PtR(Cl)(DMSO),] in the solid state. The DMSO ligands are easily displaced by a variety of N, P, As and Sb donors.
The introduction of alkyl or aryl ligands into platinum(I1) complexes normally requires the conversion of the usual starting material K1[PtC14J into an uncharged complex [PtC12L2] [where, for example, L = PR, or ‘/z COD (COD = cycloocta-l,&diene)], which is usually isolated and purified before treatment with an organometallic reagent. Work in this laboratory has shown that the tin compounds SnMesR are convenient reagents for conversion of Pt-Cl into I%--R, especially when the Pt-Cl bond is activated as in [PtCl,(COD)] [l]. We now report that the tin compounds react with cis-[PtCl,(DMSO),] (DMSO = dimethylsulphoxide) which can be obtained in situ from K2 [PtC14] in DMSO. Typically, Kz [PtC14J (2 mmol) was dissolved in DMSO (8 cm3) at room temperature, an excess of SnMe,R (R = Me, aryl; 4-10 mmol) added, and the mixture stirred for several hours at 70-90°C. After removal of DMSO under vacuum at 7O*C, the complex was isolated by stirring with diethyl ether and recrystallising the solid thus obtained from dichloromethane/ether. This procedure gave the pure complexes cis-[PtRz(DMSO)z] in good yields (Table 1); experiments in which the products were examined before recrystallisation or in which they were converted into phosphine complexes showed that the diary1 complexes *No
reprints
available.
c20
2,2’-bipyridyl, PPh3, 1,2-bis(diphenylphosphino)ethane, P (OPh),, AsPhs, and SbPh3 to form the corresponding organoplatinum complexes of these ligands. These displacements may be carried out after isolation of the DMSO complex or directly on the mixture obtained from K,[PtC14] after removal of the excess of DMSO. Acknowledgements We thank the Commonwealth Scholarship Commission (U.K.) for a Commonwealth Academic Staff Scholarship for K.K. References 1 2
C_.Eabom, K.J. Odell and A. Pidcock. J. Chem. Sot. Dalton. (1978) 357. J.H. Price. AX. Williamson. R.F. Schramm end B.B. Wayland. Inorg. Chem..
11 (1972)
1280.
Preliminary communication
ALKYL- AND ARYL-PLATINUM(H) COMPLEXES FROM K2 [PtCL] AND TETRAORGANOTIN COMPOUNDS IN DIMETHYLSULPHOXIDE. PREPARATION AND REACTIONS OF COMPLEXES [PtR*(DMSO)* ] AND EPtR(C) (DMSO),I ’
COLIN EABORN*,
KALIPADA
School of Molecular Sciezces,
KUNDU
and ALAN PIDCOCK*
University of Sussex, Brighton BhrI 9QJ (Great Britain)
(Received February 14th, 1979)
Summary The reaction between Kz [PtCl,] and a variety of tetraorganotin compounds SnMe3R (R = Me, aryl) in DMSO gives the complexes cis-[PtR,(DMSO),] and in which the DMSO ligands are bound to Pt through S trans-[PtR(Cl)(DMSO),] in the solid state. The DMSO ligands are easily displaced by a variety of N, P, As and Sb donors.
The introduction of alkyl or aryl ligands into platinum(I1) complexes normally requires the conversion of the usual starting material K1[PtC14J into an uncharged complex [PtC12L2] [where, for example, L = PR, or ‘/z COD (COD = cycloocta-l,&diene)], which is usually isolated and purified before treatment with an organometallic reagent. Work in this laboratory has shown that the tin compounds SnMesR are convenient reagents for conversion of Pt-Cl into I%--R, especially when the Pt-Cl bond is activated as in [PtCl,(COD)] [l]. We now report that the tin compounds react with cis-[PtCl,(DMSO),] (DMSO = dimethylsulphoxide) which can be obtained in situ from K2 [PtC14] in DMSO. Typically, Kz [PtC14J (2 mmol) was dissolved in DMSO (8 cm3) at room temperature, an excess of SnMe,R (R = Me, aryl; 4-10 mmol) added, and the mixture stirred for several hours at 70-90°C. After removal of DMSO under vacuum at 7O*C, the complex was isolated by stirring with diethyl ether and recrystallising the solid thus obtained from dichloromethane/ether. This procedure gave the pure complexes cis-[PtRz(DMSO)z] in good yields (Table 1); experiments in which the products were examined before recrystallisation or in which they were converted into phosphine complexes showed that the diary1 complexes *No
reprints
available.
c20
2,2’-bipyridyl, PPh3, 1,2-bis(diphenylphosphino)ethane, P (OPh),, AsPhs, and SbPh3 to form the corresponding organoplatinum complexes of these ligands. These displacements may be carried out after isolation of the DMSO complex or directly on the mixture obtained from K,[PtC14] after removal of the excess of DMSO. Acknowledgements We thank the Commonwealth Scholarship Commission (U.K.) for a Commonwealth Academic Staff Scholarship for K.K. References 1 2
C_.Eabom, K.J. Odell and A. Pidcock. J. Chem. Sot. Dalton. (1978) 357. J.H. Price. AX. Williamson. R.F. Schramm end B.B. Wayland. Inorg. Chem..
11 (1972)
1280.