Reactions of alkynyl- and alkenylplatinum(II) compounds. 2. Study of the reaction between anhydrous hydrogen chloride and diethynylbis(dimethylphenylphosphine)platinum(II). Evidence for platinum-stabilized vinyl cations
Reactions of alkynyl- and alkenylplatinum(II) compounds. 2. Study of the reaction between anhydrous hydrogen chloride and diethynylbis(dimethylphenylphosphine)platinum(II). Evidence for platinum-stabilized vinyl cations
复制标题
炔基和烯基铂(II) 化合物的反应。
DOI：
10.1021/ic50169a039
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发表时间：
1977
期刊：
影响因子：
--
通讯作者：
M. Chisholm
中科院分区：
文献类型：
--
作者：
R. Bell;M. Chisholm
The molecular structure of III deduced from x-ray studies reveals a long vinylic C-Cl bond distance, 1.809 (6) Á, and a large Pt-CC angle, 133.5. The decomposition of III to give IV and acetylene occurs much faster in CD2C12 and CDC13 than in benzene. The reaction III-* IV+ HC= CH is slow relative to HC1 elimination from III, irrespective of the solvent. A mixture of III and III-d^ decomposes in themelt and in solution to give a mixture of acetylene-d0,-d\, and-d2. An isotope ratio kH/kD=* 1.9 has been found for the reaction III-* IV+ acetylene. A number of mechanisms which could yield acetylene in the above reaction are discussed. These findings are compared to solvolysis and elimination reactions of aryl-substituted vinyl compounds, Ar (X) C= CH2, where X= Cl, Br, or CF3S03. Platinum (II) is thus shown to greatly activate the-coordinated unsaturated organic ligand.
