PHOSPHORANEIMINATO COMPLEXES OF ZINC WITH HYDRIDE, ALKYNYLO, ALKENYLO, AND AMIDO LIGANDS

Synthesis and properties of the phosphoraneiminato complexes [ZnCl(NPM e3)](4) (1), [ZnH(NPMe3)](4) (2) as well as of the alkynylo derivative s [Zn(C=CSiMe3).(NPMe3)](4) (3), [Zn(C=C-C=C-SiMe3)(NPR3)](4) [R = Me (4a), R = Et (4b)], [Zn(C=C-Ph)(NPMe3)](4) (5) and of the alkenylozinc complexes [Zn(CH=CHMe)(NPR3)](4) [R = Me (6a), R = Et (6b)] are descr ibed. According to crystal structure analyses of 1, 3, and 4b these co mplexes possess hetero-cubane 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 disintegr ation of the heterocubanes and formation of the dimeric complex [Zn(mu (2)-NPEt3){N(SiMe3)(2)}](2) (7) and of the trinuclear derivative [Zn-3 (mu(2)-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-cycl ic fashion. 7 and 8 are also characterized by crystal structure analys es.