Oxy-and Thio Phosphorus Acid Derivatives of Tin. IX. Di- and Triorganotin (IV) Diphenylphosphate Esters

摘要

Six triorgano- and five diorganotin(IV) diphenylphosphates, R3SnO2P(OC6H5)2 where R = CH3, C2H5, n-C3H7, n-C4H9, C6H5 and cyclo-C6H11, and R2Sn(O2P(C6H5)2)2 where R = CH3, C2H5, n-C4H9, C6H5 and n-C8H17, are synthesized by five routes: elimination of water by condensation of diphenylphosphoric acid with triorganotin(IV) hydroxides (R = CH3, C6H5 and cyclo-C6H11), bis-(triorganotin(IV) oxide (R = n-C3H7, n-C4H9), or diorganotin(IV) oxides (R = CH3, n-C4H9, n-C8H17, C6H5) where the released water is removed azeotropically to drive the reactions forward, or by precipitation of sodium chloride from the reaction of sodium diphenylphosphate with tri- (R = C6H5) or diorganotin(IV) (R = C2H5) chlorides. The products are crystalline solids, soluble in polar and non-polar solvents, except for the triorganotin(IV) derivatives below R = CH3 which are oils. An NMR <2J(119Sn-C-1H) coupling constant of 73.0Hz is consistent with a five-coordinated structure for the trimethyltin(IV) derivative in solution. In none of the mass spectra are there parent molecular ions, ions of mass higher than the parent, or any di- or polytin-bearing species, thus ruling out association in the gas phase. The highest mass fragments derive from the loss of one organic group from tin from the tri- and from the loss of one ligand moiety from the diorganotin derivatives. Successive loss of phenyl groups can be seen in the phenyltin spectra.