Andrew Behrle - Formation of a Bridging Phosphinidene Thorium Complex

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  Publication Details (including relevant citation   information):

    Department of Chemistry, University of Missouri, Columbia, Missouri     65211, United States 
    Universite de Toulouse     and CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO, 135     Avenue de Rangueil, F-31077 Toulouse, France 
  J. Am. Chem. Soc., 2015, 137 (47), pp 14846–14849
  DOI: 10.1021/jacs.5b09826


  The synthesis and structural determination of the first thorium   phosphinidene complex are reported. The reaction of 2 equiv of   (C5Me5)2Th(CH3)2  with   H2P(2,4,6-iPr3C6H2)   at 95 °C produces   [(C5Me5)2Th]22-P[(2,6-CH2CHCH3)2-4-iPrC6H2]   as well as 4 equiv of methane, 2 equiv from deprotonation of the   phosphine and 2 equiv from C–H bond activation of one methyl   group of each of the isopropyl groups at the 2- and 6-positions.   Transition state calculations indicate that the steps in the   mechanism are P–H, C–H, C–H, and then P–H bond activation to form   the phosphinidene.

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