Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen. LXXVIII. Das Verhalten von monomeren und dimeren Thiophosphinitonickel-Komplexen gegenueber Alkinen und Phosphaalkinen

Article abstract of DOI:10.1016/0022-328X(92)83473-U

Depending on the steric demand of the phosphorus bound substituents, the action of the secondary phosphine sulphides R2P(H)S (1a-h) (R=Me (a), Et (b), i-Pr (c), t-Bu (d), Ph (e), Xyl (f), Mes (g), Cy (h)) on nickelocene results in the formation of either the dimeric complexes <(η⁵-C5H5)Ni(μ-S=PR₂)>2 (2a-c, e, h) or the monomeric thiophosphinito complexes (η⁵-C5H5)Ni(η²-S=PR₂) (3d, f, g).The transition monomer <*> dimer occurs between R=Cy and t-Bu.In addition to 3d, f, g, the mixed ligand complexes (R₂PS2)Ni(η²-S=PR₂) (4d, f, g) are formed.H3CO2CC<*>CCO2CH3 cyclo-codimerizes with the P=S function in the xylyl and mesityl compounds 3f, g with formation of the S-isomeric thiaphosphanickelacyclopentadienes (5f, g).By way of contrast with the phosphaalkyne t-BuC<*>P the P=S bond in 3f, g is cleaved for the first time with formation of the novel thiadiphosphanickelacyclopentenes (6f, g).According to an X-ray structural analysis the planar five-membered heterocycle 6f crystallizes in the triclinic space group P<*> with Z=2, and has short P-C and C-S distances.