Diane Dickie - Reactivity of bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin with CO2, OCS, and CS2 and comparison to that of bis[bis(trimethylsilyl)amido]tin.

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      Publication Details (including relevant citation   information): Stewart,Constantine A., Dickie,Diane A.,   Parkes,Marie V., Saria,Josephat A., Kemp,Richard A., Inorg.   Chem. (Washington, DC, U. S.), 2010,   49 (23), pp 11133-11141

      Abstract: Cyclic tin(II) diamide,   [(CH2SiMe2)2N]Sn (2), an analog of the well-studied [(Me3Si)2N]Sn   (1), reacts with heterocumulenes, such as carbon dioxide (CO2),   carbonyl sulfide (OCS), and carbon disulfide (CS2) to yield an   unexpectedly diverse products. Reaction of 2 with CO2 resulted in   the formation of 2,5-disila-1-oxacyclopentane (CH2SiMe2)2O, along   with tin tetranuclear oxo-bridged cluster   Sn4(μ4-O){μ2-O2CN[SiMe2(CH2)2]}4(μ2-N:C:O)2 (4) as the primary   organometallic Sn-contg. product. The reaction of 2 with CS2 led   to formal redn. of CS2 to bridging [CS2]2-, yielding   [{[(CH2)Me2Si]2N}2Sn]2(μ3-CS2){[(CH2)Me2Si]2N}2Sn (5), in which   the [CS2]2- is coordinated through C and S to two tin centers.   The product 5 also contains a novel 4-membered Sn-Sn-C-S ring,   and exhibits a further bonding interaction through sulfur to a   third Sn atom. Reaction of OCS with 2 resulted in an insol.   polymeric material. In a comparison reaction, the acyclic diamide   1 was treated with OCS to yield Sn4(μ4-O)(μ2-OSiMe3)5(η1-N:C:S)   (3). A combination of NMR and IR spectroscopy, mass spectrometry,   and single crystal x-ray diffraction were used to characterize   the products of each reaction. The oxygen atoms in the final   products come from the facile cleavage of either CO2 or OCS,   depending on the reacting carbon dichalcogenide. [on   SciFinder(R)]

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