The reaction of the tertiary phosphine sulfides R3PS (R = Ph, Me2N or C6H11) with X2 (X2 = I2, Br2, IBr or ICl); structural characterisation of the CT complexes (Me2N)3PSI2 and Ph3PS(I0.89Br0.11)Br and the ionic compound [{(Me2N)3PS}2S]2+ 2[Br3]–

摘要: The reactions of the tertiary phosphine sulfides R3PS (R = Ph, Me2N or C6H11) with X2 (X = I Br) and IX (X = Br Cl) have been studied. Reaction I2 results in quantitative isolation CT complexes R3PSIX (X = I, Br Cl), except for Ph3PS which produces unusual compound (Ph3PSI2)2I2, has crystallographically characterised by earlier workers. crystal structure (Me2N)3PSI2 determined compared to Ph3PSI2, previously described. greater d(I–I) (Me2N)3PSI2, 2.856(1) A, that 2.823(1) A Ph3PSI2 clearly illustrates R3PSI2 compounds is sensitive R, although this effect less pronounced when analogous R3PSeI2 compounds. product from reaction IBr also represents first example a sulfide interhalogen complex. It formula Ph3PS(I0.89Br0.11)Br isomorphous Ph3PSI2. Br2 In case Ph3PS, phosphorus–sulfur bond cleavage occurs quantitatively produce Ph3PBr2 elemental sulfur. (Me2N)3PS gives, as one product, [{(Me2N)3PS}2S][Br3]2 moderate (ca. 30%) yield. This dication reported [(But3PTe)2Te][SbF6]2. Tricyclohexylphosphine reacts solvents low relative permittivity (Et2O) 1∶1 addition complex (C6H11)3PSBr2; however, dissolution material higher (C6H11)3PBr2