Oxidation and chalcogenylative disproportionation of anionic phosphide ligands in yttrium complexes with elemental sulfur and selenium

The oxidation and disproportionation of anionic phosphinato ligands in yttrium complexes with elemental sulfur and selenium were reported. The mixed TpMe2/Cp supported yttrium phosphinate complex TpMe2CpYPPh2(THF) (1) reacted with one equiv of elemental S or Se in THF at room temperature to deliver two structurally characterized yttrium dithio- or monoseleno-phosphinates TpMe2CpYS2PPh2(THF) (2) and TpMe2CpYSePPh2(THF) (4Se), respectively. Further investigations showed that the yttrium thiophosphinate TpMe2CpYSPPh2(THF) (4S) can be isolated from the reactions of 2 and 1 or 1 and elemental S in short reaction time. Moreover, Staying 4S or 4Se in THF solution for some days, 2 or [(TpMe2)2Y]+[Se2PPh2]- (5) were obtained by a disproportionation process. The mechanism for the construction of the Ph2PE- and Ph2PE2- (E = S, Se) ligands have been discussed based on the in situ NMR experiments and some designed reactions. TpMe2CpYS2PPh2(THF) (2) and TpMe2CpYSePPh2(THF) (4Se), respectively. Further investigations showed that the yttrium thiophosphinate TpMe2CpYSPPh2(THF) (4S) can be isolated from the reactions of 2 and 1 or 1 and elemental S in short reaction time. Moreover, Staying of 4S or 4Se in THF solution for some days, 2 or [(TpMe2)2Y]+[Se2PPh2]- (5) were obtained by a disproportionation process. The mechanism for the construction of the Ph2PE- and Ph2PE2- (E = S, Se) ligands have been discussed based on the in situ NMR experiments and some designed reactions.