Homometallic rare-earth metal phosphinidene clusters: Synthesis and reactivity

Abstract

Two new trinuclear μ3-bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3(μ3-Me)(μ3- PPh)] (L=[PhC(NC6H4iPr2-2,6)2] -, Ln=Y (2 a), Lu (2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho C-H bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation. A rare gathering: Two new trinuclear μ3-bridged rare-earth metal phosphinidene complexes were synthesized by treatment of the corresponding carbene precursors with phenylphosphine; some new transformation patterns of phosphinidenes are revealed. A possible pathway for reaction of these phosphinidene complexes with CS2 was determined by DFT calculations. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.