The reactions of alkyltrimethylphosphinenickel complexes with isocyanides and alkynes |
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| Institution: | 1. Department of Chemistry, Faculty of Science, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia;1. Faculty of Life and Medical Sciences, Doshisha University, Kyotanabe 610-0321, Japan;2. Faculty of Pharmaceutical Sciences, Suzuka University of Medical Science, Suzuka 513-8670, Japan;1. Lehrstuhl für Anorganische Chemie I, Chemistry Department, Bielefeld University, Universitätsstr. 25, 33615 Bielefeld, Germany;2. Lehrstuhl für Biochemie III, Chemistry Department, Bielefeld University, Universitätsstr. 25, 33615 Bielefeld, Germany;3. Lehrstuhl für Experimentelle Biophysik, Physics Department, Bielefeld University, Universitätsstr. 25, 33615 Bielefeld, Germany |
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| Abstract: | t-Butylisocyanide reacts with NiRCl(PMe3)2 (R CH3, Ia; R CH2SiMe3, Ib) to give, successively, the products of mono- and di-insertion into the nickelcarbon bonds; with more than two equivalents of isocyanide, trimethylphosphine ligands are displaced. In contrast to related palladium reactions, cyclohexyl isocyanide gives mono-insertion products only, while benzyl isocyanide is polymerised. The reactions of diphenylacetylene with Ia and Ib in methanol give (Z) vinylnickel complexes, trans-Ni{C(Ph)C(Ph)R}Cl(PMe3)2, while from reaction in diethyl ether a precursor complex NiMeCl(PMe3)2 · (PhCCPh)0.5] can be isolated. On heating the (Z)-vinyl complexes come into thermodynamic equilibrium with their (E)-isomers. The vinyl complexes are stereochemically rigid and resistant to further insertion. |
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