Derivatives of bivalent germanium, tin, and lead. Part X. Tin(II) bis(phenoxides), bis(O-methyl dithiocarbonate), and bis(diethyidithiocarbamate)

Abstract

Tin(II) bis(phenoxides), Sn(OR)2(I), have been synthesised in high yield from bis(methylcyclopentadienyl)tin and 2 mol of phenol in benzene or tetrahydrofuran (thf); o-aminophenol yields a compound of composition Sn2(OR)3 due to some Sn–N covalent bond formation. The reaction of Sn(OMe)2 with phenols does not give (I), but [(p-MeC6H4O)SnOSn(OC6H4Me-p)], (IV), has been isolated from the reaction with p-cresol. Mossbauer spectra of the compounds (I) and (IV) indicate the presence of polymeric lattices in which adjacent tin atoms are bridged by oxide and phenoxide oxygen atoms in an infinite array. Tin(II) bis(diethyldithiocarbamate), [Sn(S2CNEt2)2], and bis(O-methyl dithiocarbonate), [Sn(S2COMe)2], have been obtained by metathesis between tin(II) chloride and K[S2CNEt2] or K[S2COMe]. The Mossbauer parameters for the dithiocarbonate are substantially different from those for the diethyldithiocarbamate which is known to possess a structure based on a distorted trigonal bipyramid with the tin lone pair occupying a sp2 hybrid orbital, and suggests a structure in which dithiocarbonate chelates the tin atoms in such a way that the four sulphur atoms are disposed almost tetrahedrally about the metal.