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Vanadium and niobium diamidophosphine complexes and their reactivity

TitleVanadium and niobium diamidophosphine complexes and their reactivity
Publication TypeJournal Article
Year of Publication2003
AuthorsShaver, MP, Thomson, RK, Patrick, BO, Fryzuk, MD
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume81
Pagination1431-1437
Date PublishedDec
Type of ArticleArticle
ISBN Number0008-4042
Keywords3-COORDINATE MOLYBDENUM(III), BRIDGING N-2 UNIT, COORDINATION, COORDINATION CHEMISTRY, DINITROGEN COMPLEX, END-ON, FUNCTIONALIZATION, HYDROGENATION, LIGAND, METATHESIS, NIOBIUM, REDUCTION, REDUCTIVE CLEAVAGE, SIDE-ON, TANTALUM COMPLEX, VANADIUM
Abstract

The tridentate ligand precursors R’P(CH2SiMe2NR")(2) ((R’R’’)[NPN]: R’ = Cy, Ph; R" = Ph, Mes, Me) were prepared from metathesis reactions of a lithiated amine, chloro(chloromethyl)dimethylsilane, the appropriate 1degrees phosphine, and n-butyl lithium and were isolated as solvent adducts. Metathesis between (CyPh)[NPN]Li-2(OEt2), 2, and VCl3(THF)(3) afforded ((CyPh)[NPN]VCl)(2), 7, whose solid-state structure was established by X-ray crystallography. Reduction attempts of the ((R’R’’)[NPN]VCl)(2) species with KC8 incorporated molecular nitrogen but were complicated by imide formation and ligand decomposition. Metathesis of 2 with NbCl2Me3 afforded the highly unstable complex (CyPh)[NPN]NbMe3, 15. Attempts to hydrogenate this species were unsuccessful.

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