Preparation and properties of metallacyclobutanes of nickel and palladium |
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| Authors: | Akira Miyashita Mayumi Ohyoshi Hiroaki Shitara Hiroyuki Nohira |
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| Institution: | Department of Applied Chemistry, Faculty of Engineering, Saitama University, Shimo-ohkubo 255, Urawa, Saitama 338 Japan |
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| Abstract: | Bis(phosphine)-3,3-dimethylnickela- and palladacyclobutanes have been prepared by intramolecular C-H insertion reaction of the corresponding dineopentyl metal complexes. Nickelacyclobutane complexes decompose when heated thereby undergoing competitive carbon-carbon bond cleavage to give isobutene and ethylene, with reductive elimination affording 1,1-dimethylcyclopropane and skeletal isomeri-zation of the metallacyclic ring yielding 3-methyl-1-butene, whereas the palladium analog gave no significant amounts of CC bond cleavage products.Added phos-phine was seen to have an effect on CC bond scission of nickelacyclobutane complexes. Nickelacyclobutane complexes in solution are thought to be in equilibrium with olefin-coordinated nickel-carbene complex on the basis of available experimental evidence from hydrogenolysis, carbene-trap reactions with olefins and reaction with carbon monoxide |
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| Keywords: | Author to whom correspondence should be addressed |
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