Neutral and Cationic Vanadium(III) Alkyl and Allyl Complexes with a Cyclopentadienyl-amine Ancillary Ligand
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Abstract
The (N,N-dimethylaminoethyl)cyclopentadienyl vanadium(III) complex [η5,η1-C5H4(CH2)2NMe2]VCl2(PMe3) (1), in which the pendant amine is coordinated to the metal center, was prepared by the reaction of VCl3(PMe3)2 with Li[C5H4(CH2)2NMe2] in THF. Reaction of 1 with 2 equiv of MeLi yields [η5-C5H4(CH2)2NMe2]VMe2(PMe3)2 (2), in which the amine is released in favor of the binding of a second phosphine. Compound 2 reacts with [PhNMe2H][BPh4] to form the ionic complex {[η5,η2-C5H4(CH2)2N(Me)CH2]V(PMe3)2}[BPh4] (3), in which a methyl group of the pendant NMe2 functionality is metalated, and 2 equiv of methane. Reaction of 1 with allylmagnesium chloride yields [η5-C5H4(CH2)2NMe2]V(η3-C3H5)Cl(PMe3) (4), in which the amine is released in favor of the η3-bonding of the allyl ligand. Methylation of 4 to yield thermally labile [η5-C5H4(CH2)2NMe2]V(η3-C3H5)Me(PMe3) (5), followed by reaction with [PhNMe2H][BPh4], gives protonation exclusively at the methyl group to yield the ionic allyl complex {[η5,η1-C5H4(CH2)2NMe2]V(η3-C3H5)(PMe3)}[BPh4] (6) without concomitant NMe2 metalation.
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