Diane Dickie - Insertion of CO2 into divalent group 2 and 12 bis(silylamides).

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      Publication Details (including relevant citation   information): Felix,Ana M., Boro,Brian J., Dickie,Diane   A., Tang,Yongjun, Saria,Josephat A., Moasser,Bahram,   Stewart,Constantine A., Frost,Brian J., Kemp,Richard A., Main   Group Chem., 2012, 11 (1), pp   13-29

      Abstract: Previous studies have shown that CO2   can insert into divalent Sn and Ge bis(silylamides) to give   mixts. of silylated isocyanates and bis(silyl)carbodiimides,   albeit rather sluggishly. In order to more effectively utilize   the divalent metal bis(silylamides) in synthesis, more active and   selective reactions to form only isocyanates or carbodiimides   were needed. Authors have now shown that the more electropos.   Group 2 complexes react with CO2 virtually instantaneously under   the very mild conditions of room temp. and atm. pressure CO2. It   is also demonstrated that CO2 can react under high pressure   directly with the solid Mg bis(silylamides) to produce an   unusual, high m.p. solid. Different products are obtained when   the cyclic, tied-back complex Mg[N(SiMe2CH2)2]2(Et2O)2 is used in   place of Mg[N(SiMe3)2]2(THF)2. Various Zn bis(silylamides) can be   designed to afford either the silyl isocyanate or the   bis(alkyl)carbodiimide in near quant. conversions in ~100%   selectivities. Lastly, it is shown that the tied-back Zn complex   can react with CO2 at room temp. and 4 atm CO2 pressure to cleave   CO2 and generate a product contg. a stable, [Zn4O]6+ core with a   bridging μ4-O atom. [on SciFinder(R)]

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