期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 54, 期 21, 页码 6315-6319出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201501256
关键词
manganese; methylenephosphonium ligands; P ligands; photochemical demetalation; pincer ligands
资金
- CNRS
- PICS [4873 (CNRS)/09-03-91060]
- Russian Scientific Foundation [14-13-00801]
- IDEX-UNITI
Half-sandwich manganese methylenephosphonium complexes [Cp(CO)(2)Mn((2)-R2PC(H)Ph)]BF4 were obtained in high yield through a straightforward reaction sequence involving a classical Fischer-type manganese complex and a secondary phosphine as key starting materials. The addition of various nucleophiles (Nu) to these species took place regioselectively at the double-bonded carbon center of the coordinated methylenephosphonium ligand R2P+C(H)Ph to produce the corresponding chiral phosphine complexes [Cp(CO)(2)Mn((1)-R2PC(H)(Ph)Nu)], from which the phosphines were ultimately recovered as free entities upon simple irradiation with visible light. The synthetic potential of this umpolung approach is illustrated herein by the preparation of novel chiral pincer-type phosphine-NHC-phosphine ligand architectures.
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