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Contrasting cyclo-P3 Ligand Transfer Reactivity of Valence-Isoelectronic Aryloxide Complexes [(P3)Nb(ODipp)3] and [(P3)W(ODipp)3]

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Abstract

Reduction of mer-Cl3W(ODipp)3 with Na/Hg in the presence of P4 in toluene afforded the orange complex (η3-P3)W(ODipp)3 (δinline image = –156 ppm, 10 % isolated yield). Unlike the valence-isoelectronic anion [(η3-P3)Nb(ODipp)3], treatment with AsCl3 of the neutral (η3-P3)W(ODipp)3 did not transfer the cyclo-P3 ligand to generate AsP3. Instead, this complex underwent aryloxide ligand transfer to form the red complex (η3-P3)W(Cl)(ODipp)2(THF) (δinline image = –143 ppm, 32 % isolated yield).

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