THERMAL DIMERIZATION OF 1-SUBSTITUTED-3,4-DIMETHYLPHOSPHOLES WITHIN THE COORDINATION SPHERE OF PLATINUM(II)
UNSPECIFIED. (1994) THERMAL DIMERIZATION OF 1-SUBSTITUTED-3,4-DIMETHYLPHOSPHOLES WITHIN THE COORDINATION SPHERE OF PLATINUM(II). INORGANIC CHEMISTRY, 33 (1). pp. 109-117. ISSN 0020-1669Full text not available from this repository.
The thermolyses of dihalobis(1-substituted-3,4-dimethylphosphole)platinum(II) complexes were investigated in 1,1,2,2-tetrachloroethane solutions at 145 degrees C and in the crystalline state at 140 degrees C. Three types of species were formed: (1) [4 + 2] cycloaddition products, (2) [2 + 2] cycloaddition products, and (3) compounds that result from 1,5-hydrogen migration from a methyl group on one phosphole to the beta-carbon of an adjacent phosphole (exomethylene). Kinetic studies suggest that the reaction mechanisms are the same in both the solid and solution states and that the products emanate from a common biradical intermediate. The solid-state reactions show a high degree of topotacticity with the exo-methylene products being ultimately formed in quantitative yields after about 24 h at 140 degrees C, Though the reactions in solution are slightly faster than those in the solid state, the latter are more selective. The relative reaction rates and product distributions are functions of both the phosphorus substituent and the halide. A representative example of each complex type has been characterized by single-crystal X-ray crystallography.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Journal or Publication Title:||INORGANIC CHEMISTRY|
|Publisher:||AMER CHEMICAL SOC|
|Official Date:||5 January 1994|
|Number of Pages:||9|
|Page Range:||pp. 109-117|
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