O-trialkylstannyl oximes

Article abstract of DOI:10.1021/ic50083a034

Fourth-group oximes have been synthesized from (a) the organoelement chlorides and the oxime in the presence of a strong Lewis base, (b) organotin chlorides with the O-lithio oxime to split out lithium chloride, and (c) bis(organotin) oxides and organotin hydroxides, ethoxides, and diethylamines with the oxime to split out water, ethanol, and diethylamine, respectively. The products are monomeric in solution; all are liquids except O-trimethylstannylcyclohexanone oxime whose ir spectrum differs from that in solution and whose mass spectrum shows peaks above the parent mass which are revealed by high-resolution work to contain the Sn-O-Sn backbone, presumably resulting from cyclic Sn-O-Sn-O structures in the solid. Confirmation of the high-coordination solid state structure comes from Sn^119m M?ssbauer quadrupole splitting values which are ca. 1 mm/sec higher for the trimethyltin derivatives. The O-trialkyltin oximes undergo metathetical reactions with water and hydrogen chloride and with other fourth group chlorides to give the silicon and germanium analogs, and insertion reactions with isocyanates, isothiocyanates, chloral, bromal, etc., to give novel adducts where reactivity is seen to be in the orders Sn > Ge ? Si and SnOR > SnON=C < and X₃CCHO > C₆H₅NCO > RNCO > C₆H₅NCS.