Bis(tert-butylamido)- and bis(arylamido)cyclodiphosph(III)azane complexes of Ti, V, Zr and Hf: ligand substituent effects and coordination number

Syntheses and structures of [{(ButNP)2(ButN)2}MCl2], M = Zr, Hf, [{(ButNP)2(ArN)2}TiCl2], Ar = Ph, m-Tol, pTol, and of [{(ButNP)2(PhN)2}VCl·THF], are reported. In the solid-state these compounds are seco-heterocubic metal complexes featuring one 3-coordinated bis(amido)cyclodiphosphazane ligand. When ZrCl4 and HfCl4 are treated with {(ButNP)2(PhNLi·THF)2}, however, the diligand complexes [{(ButNP)2(PhN)2}2M], M = Zr, Hf are isolated.