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. Mössbauer 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 Mössbauer 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.