title: 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(NC6 H4 iPr2 -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.
authors: Department of Chemistry, Fudan University, Shanghai 200433 (China).
authors: Kai
authors: K
authors: Wang
authors: Gen
authors: G
authors: Luo
authors: Jianquan
authors: J
authors: Hong
authors: Xigeng
authors: X
authors: Zhou
authors: Linhong
authors: L
authors: Weng
authors: Yi
authors: Y
authors: Luo
authors: Lixin
authors: L
authors: Zhang
keywords: CS2 activation; CH activation; density functional calculations; phosphinidenes; rare earths