Studies in the organonitrogen chemistry of tin and neighbouring elements

• Main Author: Othen, David George
• Published: Durham University 1977
• Subjects: 541
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.467860

This thesis describes the preparation and properties of some new organonitrogen derivatives of silicon, germanium, and tin. The structural implications of their I.R., (^1)H-NMR. , and mass spectra are discussed with X-ray crystal structures in some cases. A survey of species containing tin-nitrogen bonds, and a discussion of the stereochemistry of tin are also presented. New methyleneamine derivatives of the type (R(_2)CN)(_n)Sn(^IV)C1(_4-n)(n = 2-4), (Ph(_2)CN)(_2)GeC1(_2), [(R(_2)CN)(_2)Sn(^11)](_n),(Ph(_2) CNSn(^11)c1)(_2), and Li(^t)Bu(_2)CN)(_3)Sn(^11) were prepared from the metal chlorides and N-lithioketimines. The adducts Ph(_2)CNH.Sn(^11)Cl(_2), ((^t)Bu(_2)CNH)(_n)Sn(^IV)Cl(_4) (n = 1,2), Ph(_2)CNH. (Ph(_2)CNSn(^11)Cl)(_2). C(_7)H(_8), and (^t)Bu(_2)CNH. (^t)Bu(_2)CNSn(^11)(_2)C1(_3) are described. Attempts to prepare (^t)Bu(_2)CNSn(^IV) led to (^t)BuCN and Sn(^11)Cl(_2). Similar decomposition of ((^t)Bu(_2)CN)(_n)Sn(^IV)c1(_4-n) (n = 2,3) 2,3) led to the imino-tin(II) complexes (^t)Bu(_2)CNH. (^t)Bu(_2)CNSn(_2)(^11)Cl(_3) and (^t)Bu(_2)CNH(_2)(^+). ((^t)Bu(_2)Sn(_3)(^11)C1(_5)(^-). The new M(^IV) derivatives are monomeric, except for the iminotin chlorides [(ph(_2)CN)(_n)Sn(^IV)C1(_4-n)](_m)(n = 2,3; m ≥ 2). The Sn(^11) derivatives are mostly di- or oligomeric, containing three-coordinate tin. Association appears to involve bridging methyleneamino groups. The adducts R(_2)CNH. (R(_2)CN)(_n)Sn(_2)(^11)C1(_4-n) to contain one three-coordinate and one four- coordinate tin atom. The C=N-M skeletons of those compounds containing terminal methyleneamino groups are probably bent with little or no N→M (p→d) π-bonding.