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 1° phosphine, and n-butyl lithium and were isolated as solvent adducts. Metathesis between CyPh[NPN]Li2(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.Key words: vanadium, niobium, metathesis, coordination chemistry, reduction, hydrogenation.
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