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

TitleDiamidophosphine complexes of niobium(III) and (IV): imide formation via ancillary ligand decomposition
Publication TypeJournal Article
Year of Publication2003
AuthorsFryzuk, MD, Shaver, MP, Patrick, BO
JournalInorganica Chimica Acta
Volume350
Pagination293-298
Date PublishedJul
Type of ArticleArticle
ISBN Number0020-1693
KeywordsALKYNES, COORDINATION, diamidophosphine ligands, imido, MECHANISM, MEDIATED IMINE METATHESIS, NIOBIUM, ORGANOIMIDO COMPLEXES, REDUCTION, ROUTE, Si-N bond cleavage, tantalum
Abstract

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.

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