Darstellung,Eigenschaften sowie Reaktionen metallhaltiger Heterocyclen. LXVI. Nickelinduzierte Cyclocodimerisierung eines Thioxophosphor(V)-Kations mit einem aktivierten Alkin

Metall Containing Heterocycles: Preparation, Properties, Reactions. LXVI. Nickel Induced Cyclocodimerization of a Thioxophosphorus (V) Cation with an Activated Alkyne The action of di-tert-butylthioxophosphorane (t-Bu)₂P(H)S on nickelocene in ether results in the formation of the first kinetically stabilized (η²-diorganothioxophosphorus)nickel complex (η⁵-C₅H₅)Ni(η²-S?P(t-Bu)₂)] ( 1 ). In presence of the acetylene dicarboxylic acid dimethyl ester H₃CO₂CC? CCO₂CH₃ with (t-Bu)₂P?S a cyclocodimerization occurs with formation of the S and P isomeric thiaphosphanickelacyclopentadiene (η⁵-C₅H₅) ( 2S ) and thiaphosphanickelacyclopentene (η⁵-C₅H₅) ( 2P ) (R?CO₂CH₃), respectively. The composition and structure of the compounds 1, 2S , and 2P were determined from the mass, IR, and NMR spectra.