Diane Dickie - Reactions of carbon dioxide, carbon disulfide and carbonyl sulfide with tin(II) silylamides.

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      Publication Details (including relevant citation   information): Stewart,Constantine A., Dickie,Diane A.,   Parkes,Marie V., Kemp,Richard A., Abstracts of Papers, 237th   ACS National Meeting, Salt Lake City, UT, United States, March   22-26, 2009, 2009, pp INOR-559

      Abstract: Although   bis[bis(trimethylsilyl)amido]tin(II) {[(Me3Si)2N]2Sn} and   bis(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopent-1-yl)tin   [(tmdacp)2Sn] are almost identical electronically, their   different steric properties lead to unexpectedly diverse chem.   with CO2, OCS and CS2. For example, OCS and [(Me3Si)2N]2Sn react   slowly to give Sn4(mu4-O)(mu2-NSiMe3)5(O=C=S). This cluster, the   first structurally characterized metal-carbonyl sulfide complex,   contains both Sn(II) and Sn(IV) with one tin(IV) coordinated to   the carbonyl sulfide through the oxygen. The smaller (tmdacp)2Sn   is generally more reactive. The reaction of (tmdacp)2Sn with CO2   was rapid and yielded a Sn4(mu4-O) cluster   Sn4(mu4-O)(mu2-O2C(tmdacp)4)(mu2-N=C=O)2. The two N=C=O ligands   bridge two tin atoms through the nitrogen. All tin atoms in this   cluster have been oxidized to the +4 oxidn. state. Reaction of   (tmdacp)2Sn with OCS proceeded very rapidly to produce an   intractable polymer, but with CS2 it gave a very interesting dark   green complex with three (tmdacp)2Sn mols. coordinated to one   CS2, as shown below. [on SciFinder(R)]

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