Semi-empirical SCF–MO Studies of Platinum Hydrides and the Insertion Reaction of Ethylene into the Pt(II)–H Bond
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概要
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Semi-empirical SCF–MO calculations were carried out on <I>trans</I>-PtHX(PH<SUB>3</SUB>)<SUB>2</SUB> (X= halogen and CN<SUP>−</SUP>). The absolute value of <I>E</I><SUB>pt-H</SUB> decreases in the following order: F>Cl>Br>I>CN; this agrees with the order of the bond strength of the Pt–H bond. The electron density on the H ligand is remarkably large in all the complexes (<I>ca</I>. 1.25 e) and decreases in this order: F>Cl>Br>I>CN. An insertion reaction of ethylene into the Pt–H bond was investigated by the use of the MO method. The intermediate five-coordinate π-olefinic hydride complex has a trigonal bipyramid structure in which Cl and H ligands are positioned <I>trans</I> to each other. Three reaction paths of the insertion were investigated, and the following reaction path seems the best: The H ligand starts first to approach ethylene and then the Cl ligand starts to move to the <I>trans</I>-position of the H ligand. The reactivities of <I>trans</I>-PtHX(PH<SUB>3</SUB>)<SUB>2</SUB> increase in this order: F<Cl<Br<I<CN. MO calculations also reveal that the catalytic ability of <I>trans</I>-PtHK(PH<SUB>3</SUB>)<SUB>2</SUB> increases as follows in the hydrogen-deuterium exchange reaction of ethylene: F<Cl<Br<I
- 公益社団法人 日本化学会の論文
著者
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SAKAKI Shigeyoshi
Department of Applied Chemistry & Biochemistry, Faculty of Engineering, Kumamoto University
-
Kanai Hiroyoshi
Department Of Cardiovascular Medicine Gunma University Graduate School Of Medicine
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Kato Hiroshi
Department Of Applied Biological Chemistry Graduate School Of Agricultural And Life Sciences The Uni
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Kanai Hiroyoshi
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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Tarama Kimio
Department of Hydrocarbon Chemistry, Faculty of Engineering, Kyoto University
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