Diane Dickie - Reactions of CO2 and related heteroallenes with CF3-substituted aromatic silylamines of tin.

Document created by Diane Dickie on Aug 22, 2014
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  Publication Details (including relevant citation   information): Stewart,Constantine A., Dickie,Diane A.,   Moasser,Bahram, Kemp,Richard A., Polyhedron,   2012, 32 (1), pp 14-23

  Abstract: In this report we detail the synthesis   and characterization of new Sn(II) complexes contg. the   -N[(SiMe3)(ArF)] ligand [ArF = 3,5-(CF3)2C6H3], specifically   designed to provide both an electron-withdrawing -ArF group as   well as the -SiMe3 group required for migration to oxygen. As   well, we have also examd. the reaction of the LiN[(SiMe3)(ArF)]   precursor with CO2 and obsd. the formation of a bicyclic lithium   carbamate consisting of two 8-membered rings characterized by   single crystal x-ray crystallog. The desired starting complex   Sn[N(SiMe3)(ArF)]2 could be prepd. directly via a metathesis   reaction, although x-ray quality crystals could not be grown. The   reactions of this complex with CO2, OCS, and CS2 are described.   Reaction with CO2 results in an unexpected insertion reaction   quite dissimilar to those seen in the literature. A proposed   route that explains the surprising CO2 reaction chem. and   products is given. Reactions of Sn[N(SiMe3)(ArF)]2 with OCS led   to multiple products, while reaction with CS2 led to simple   insertion to form a dithiocarbamate. Interestingly, an attempt to   purify Sn[N(SiMe3)(ArF)]2 by distn. led to an unexpected   cyclization reaction with activation of an arom. H atom. This   ortho-metalated product from this cyclization reaction was   clearly identified via x-ray crystallog. [on SciFinder(R)]

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