LAUSR

The oxidation and disproportionation of anionic phosphide ligands in yttrium complexes with elemental sulfur and selenium are reported. The mixed TpMe2/Cp supported yttrium phosphide 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 a short reaction time. Moreover, after keeping 4S or 4Se in THF solution for some days, 2 or [(TpMe2)2Y]+[Se2PPh2]- (5) was obtained by a disproportionation process. The mechanism for the construction of the Ph2PE- and Ph2PE2- (E = S, Se) ligands has been discussed based on the in situ NMR experiments and some designed reactions.