1309826-25-2Relevant articles and documents
Reactions of CO2 and related heteroallenes with CF 3-substituted aromatic silylamines of tin
Stewart, Constantine A.,Dickie, Diane A.,Moasser, Bahram,Kemp, Richard A.
, p. 14 - 23 (2012)
In this report we detail the synthesis and characterization of new Sn(II) complexes containing the -N[(SiMe3)(ArF)] ligand [Ar F = 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 examined the reaction of the LiN[(SiMe3) (ArF) precursor with CO2 and observed the formation of a bicyclic lithium carbamate consisting of two 8-membered rings characterized by single crystal X-ray crystallography. The desired starting complex Sn[N(SiMe3)(ArF)]2 could be prepared 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 chemistry 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 distillation led to an unexpected cyclization reaction with activation of an aromatic H atom. This ortho-metallated product from this cyclization reaction was clearly identified via X-ray crystallography.
