Diamidophosphine complexes of niobium(III) and (IV): imide formation via ancillary ligand decomposition

被引:20
作者
Fryzuk, MD [1 ]
Shaver, MP [1 ]
Patrick, BO [1 ]
机构
[1] Univ British Columbia, Dept Chem, Vancouver, BC V6T 1Z1, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
niobium; diamidophosphine ligands; imido; Si-N bond cleavage; reduction;
D O I
10.1016/S0020-1693(02)01499-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The diamidophosphine complexes of niobium (CyPh)[NPN]NbCl(DME) (2), (CyPh)[NPN]NbCl2 (6), and (PhPh)[NPN]NbCl2 (9), where (RR')[NPN]=RP(CH2SiMe2NR')(2) have been prepared, isolated and characterized. Generation of (RR')[NPN]NbCl(DME) species competes with the production of ((RR')[NPN]NbCl)(2)(mu-N-2) and can be controlled with N-2 pressure. (CyPh)[NPN]NbCl2 spontaneously decomposes into (CyPh)[NPN]NbCl(=NPh) (7), CyP(CH2SiMe2)(2)NPh (8), and a paramagnetic impurity. Compound 7 was characterized by an X-ray diffraction study and its structural features are discussed. The Nb-N-imido bond length is 1.789(2) Angstrom with a Nb-N-imido-C bond angle of 167.9(2)degrees in a distorted square pyramidal structure. Reduction of (PhPh)[NPN]NbCl2 (9), with KC8 produced (PhPh)[NPN]NbCl(=NPh), PhP(CH2SiMe2)(2)NPh, and a paramagnetic impurity. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:293 / 298
页数:6
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