0000000000160733

AUTHOR

Nicolas Poujaud

Tantalocenehydridephosphorus chemistry.

Abstract The aim of this paper is to look for a better knowledge of the behaviour of bent tantalocenes that bear hydrides, phosphorus PR2X (R=Me, Ph; X=H, lone pair) and cyclopentadienyl (Cp=C5H5, Cp′=C5H2tBu(Me)2, Cp*=C5Me5) ligands. An orbital control of regioselectivity of insertion of the PR2 phosphide fragment of chlorophosphines PR2Cl into the central TaH bond of trihydrides Cp2TaH3 leading to the formation of metallophosphonium cations is discussed. Neutralisation of cationic complexes with strong bases leads either to the Ta(V)–phosphide or to the Ta(III)–phosphine species depending on the nature of the cyclopentadienyl ligand; good electron donor Cp′ and Cp* rings favour the forma…

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Synthesis and characterization of new allyl palladium complexes with thionate ligands; X-ray molecular structures of [Pd3(η3-C4H7)3{pm(Me)2S}2](CF3SO3) and [Pd{pm(Me)2S}2], η3-C4H7=η3-2-MeC3H4, pm(Me)2S=Pyridine-4,6-dimethyl-2-thionate

Abstract The reaction of [Pd(η3-C4H7)]CF3SO3 (η3-C4H7=η3-2-MeC3H4) (1), prepared in situ by reaction of [Pd(η3-C4H7)Cl]2 with AgCF3SO3, with various thionate ligands, gives new polymeric complexes formulated as [Pd(η3-C4H7)(RS)]n (2) [RS=pyS (pyridine-2-thionate)], im(Me)S(imidazole-3-methyl-2-thionate) (3), pm(Me)2S (pyrimidine-4,6-dimethyl-2-thionate) (4). A solution of 4 contaminated with KCF3SO3 evolves to give crystals that correspond to a new polymeric species whose X-ray crystal molecular structure indicates the presence of cationic infinite chains built of trinuclear units, [Pd3(η3-C4H7)3{pm(Me)2S}2]+ (5). Finally, the formation of a mononuclear thionate-containing palladium complex…

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