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- Title
Homometallic Rare-Earth Metal Phosphinidene Clusters: Synthesis and Reactivity.
- Authors
Wang, Kai; Luo, Gen; Hong, Jianquan; Zhou, Xigeng; Weng, Linhong; Luo, Yi; Zhang, Lixin
- Abstract
Two new trinuclear μ3-bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3(μ3-Me)(μ3-PPh)] (L=[PhC(NC6H4 iPr2-2,6)2]−, Ln=Y ( 2 a), Lu ( 2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho CH bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation.
- Subjects
RARE earth metals; PHOSPHINIDENES; CARBENES; TOLUENE; ISOTHIOCYANATES; WITTIG reaction
- Publication
Angewandte Chemie International Edition, 2014, Vol 53, Issue 4, p1053
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201307422