Phosphaniminato-Komplexe des Zinks mit Hydrido-, Alkinylo-, Alkenylo- und Amido-Liganden

Phosphoraneiminato Complexes of Zinc with Hydrido, Alkynylo, Alkenylo, and Amido Ligands Synthesis and properties of the phosphoraneiminato complexes ZnCl(NPMe₃)]₄ ( 1 ), ZnH(NPMe₃)]₄ ( 2 ) as well as of the alkynylo derivatives Zn(C≡C–SiMe₃)(NPMe₃)]₄ ( 3 ), Zn(C≡C–C≡C–SiMe₃)(NPR₃)]₄ R = Me ( 4 a ), R = Et ( 4 b )], Zn(C≡C–Ph)(NPMe₃)]₄ ( 5 ) and of the alkenylozinc complexes Zn(CH=CHMe)(NPR₃)]₄ R = Me ( 6 a ), R = Et ( 6 b )] are described. According to crystal structure analyses of 1 , 3 , and 4 b these complexes possess heterocubane structures with only slightly distorted Zn₄N₄ cubic skeletons. Experiments to substitute the terminal ligands at the zinc atoms by bis(trimethylsilyl)amido groups lead to disintegration of the heterocubanes and formation of the dimeric complex Zn(μ₂-NPEt₃){N(SiMe₃)₂}]₂ ( 7 ) and of the trinuclear derivative Zn₃(μ₂-NPMe₃)₄{N(SiMe₃)₂}₂] ( 8 ), in which the central zinc atom is surrounded by the four N atoms of the NPEt₃^– groups in a spiro-cyclic fashion. 7 and 8 are also characterized by crystal structure analyses.