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Published on: May 1, 2016
Oxidation and chalcogenylative disproportionation of anionic phosphide ligands in yttrium complexes with elemental
Fangjun Zhang1, Weiyin Yi1, Jie Zhang1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, People's Republic of China. zhangjie@fudan.edu.cn xgzhou@fudan.edu.cn.
Abstract:
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.
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