Homometallic Rare-Earth Metal Phosphinidene Clusters: Synthesis and Reactivity

Authors

  • Kai Wang,

    1. Department of Chemistry, Fudan University, Shanghai 200433 (China)
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  • Gen Luo,

    1. State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024 (China)
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  • Dr. Jianquan Hong,

    1. Department of Chemistry, Fudan University, Shanghai 200433 (China)
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  • Prof. Dr. Xigeng Zhou,

    Corresponding author
    1. Department of Chemistry, Fudan University, Shanghai 200433 (China)
    • Xigeng Zhou, Department of Chemistry, Fudan University, Shanghai 200433 (China)

      Yi Luo, State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024 (China)

      Lixin Zhang, Department of Chemistry, Fudan University, Shanghai 200433 (China)

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  • Prof. Dr. Linhong Weng,

    1. Department of Chemistry, Fudan University, Shanghai 200433 (China)
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  • Prof. Dr. Yi Luo,

    Corresponding author
    1. State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024 (China)
    • Xigeng Zhou, Department of Chemistry, Fudan University, Shanghai 200433 (China)

      Yi Luo, State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024 (China)

      Lixin Zhang, Department of Chemistry, Fudan University, Shanghai 200433 (China)

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  • Assoc. Prof. Dr. Lixin Zhang

    Corresponding author
    1. Department of Chemistry, Fudan University, Shanghai 200433 (China)
    • Xigeng Zhou, Department of Chemistry, Fudan University, Shanghai 200433 (China)

      Yi Luo, State Key Laboratory of Fine Chemicals, School of Pharmaceutical Science and Technology, Dalian University of Technology, Dalian 116024 (China)

      Lixin Zhang, Department of Chemistry, Fudan University, Shanghai 200433 (China)

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  • This work was supported by the NSFC, 973 Program (2012CB821604), the Ministry of Education of China. The authors also thank the Network and Information Center of Dalian University of Technology for computational resources.

Abstract

Two new trinuclear μ3-bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}33-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[BOND]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.

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