Homometallic Rare‐Earth Metal Phosphinidene Clusters: Synthesis and Reactivity

• DOI: 10.1002/anie.201307422
• Publication Date: 2013-12-05T17:37:11Z
• Authors: Kai Wang; Gen Luo; Jianquan Hong; Xigeng Zhou; Linhong Weng; Yi Luo; Lixin Zhang
• Keywords: 01 natural sciences; 0104 chemical sciences

AbstractTwo 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.