Andrew Behrle - Insertion Reactions and Catalytic Hydrophosphination of Heterocumulenes using α-Metalated N,N-Dimethylbenzylamine Rare-Earth-Metal Complexes

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      Publication Details (including relevant citation   information):

        Department of Chemistry, School of Green Chemistry and     Engineering, College of Natural Sciences and Mathematics,     The University of Toledo, 2801     W. Bancroft Street, MS 602, Toledo, Ohio 43606-3390, United     States  
      Organometallics, 2013, 32 (5), pp 1141–1149
      DOI: 10.1021/om300807k


      The reactivity of homoleptic α-metalated dimethylbenzylamine   lanthanide complexes (α-Ln(DMBA)3; Ln = La,   Y; DMBA = α-deprotonated dimethylbenzylamine) was probed through   a series of stoichiometric insertion and catalytic   hydrophosphination reactions. Both rare-earth-metal species   inserted 3 equiv of various carbodiimides to form the   corresponding homoleptic amidinates.   α-La(DMBA)3 was also found to be a useful   precatalyst for the room-temperature hydrophosphination of   heterocumulenes to form phosphaguanidines, phosphaureas, and   phosphathioureas in moderate to excellent isolated yields.   Furthermore, through a series of stepwise stoichiometric   protonation and insertion reactions, a plausible mechanism for   the hydrophosphination catalysis was investigated.

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