Diane Dickie - Activation of CO2 and CS2 by (Me3Si)(i-Pr2P)NH and its zinc complex.

Document created by Diane Dickie on Nov 17, 2015
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  Dickie, Diane A., Ulibarri-Sanchez III, Raymond P., Jarman, Paul   J., Kemp, Richard A. Polyhedron 58 92-98

  Abstract: The reaction of (Me3Si)(i-Pr2P)NH with   ZnEt2 gives {[(Me3Si)(i-Pr2P)N]ZnEt}2, which was characterized by   multinuclear NMR spectroscopy and x-ray crystallog. This Zn   complex reacts with CO2 to give an adduct with the proposed   formula of [(Me3Si)N(i-Pr2PCO2)]ZnEt that undergoes further   transformation into the crystallog. characterized di-adduct   [(Me3Si)N(i-Pr2PCO2)]2Zn, in addn. to a Zn6 cluster contg. both   P-CO2 adducts and fragments of the isocyanate i-Pr2P-NCO. These   reaction pathways were sep. obsd. in related Group 2 and Group 14   complexes, but not previously within the same mol. Reactions with   the related heteroallene CS2 were also examd. The free ligand   (Me3Si)(i-Pr2P)NH reacts with CS2 to form a bright red, cryst.   adduct (Me3Si)[P(i-Pr)2(CS2)]NH. This adduct was treated with   ZnEt2 to provide the same product that was obtained from the   reaction of {[(Me3Si)(i-Pr2P)N]ZnEt}2 with CS2, proposed to be a   dithiocarbamate complex, with the CS2 bound to the N instead of   the P atom. [on SciFinder(R)]

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