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Homometallic Rare‐Earth Metal Phosphinidene Clusters: Synthesis and Reactivity
Author(s) -
Wang Kai,
Luo Gen,
Hong Jianquan,
Zhou Xigeng,
Weng Linhong,
Luo Yi,
Zhang Lixin
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201307422
Subject(s) - phosphinidene , chemistry , phenylphosphine , reactivity (psychology) , carbene , oxide , metal , rare earth , ligand (biochemistry) , sulfide , toluene , medicinal chemistry , wittig reaction , inorganic chemistry , catalysis , organic chemistry , mineralogy , medicine , biochemistry , alternative medicine , receptor , pathology , phosphine
Two new trinuclear μ 3 ‐bridged rare‐earth metal phosphinidene complexes, [{L(Ln)(μ‐Me)} 3 (μ 3 ‐Me)(μ 3 ‐PPh)] (L=[PhC(NC 6 H 4 i Pr 2 ‐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 CS 2 leads to the formation of novel trinuclear rare‐earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation.