Abstract
t-Butylisocyanide reacts with NiRCl(PMe 3) 2 (R CH 3, Ia; R CH 2SiMe 3, 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(PMe 3) 2, while from reaction in diethyl ether a precursor complex [NiMeCl(PMe 3) 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.
Published Version
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