期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 56, 期 42, 页码 12925-12929出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201706496
关键词
carbenes; multiple bonding; organometallics; thorium; ylides
资金
- U.S. Department of Energy, Office of Science, Early Career Research Program [DE-SC-0014174]
- Humboldt Foundation
- Chinese Academy of Science
- CalMip
The reaction of (C5Me5)(2)Th(CH3)(2) with the phosphonium salts [CH3PPh3]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C5Me5)(2)Th[CHPPh3]X, rare terminal phosphorano-stabilized carbenes with thorium. These complexes feature the shortest thorium-carbon bonds (approximate to 2.30 angstrom) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X = Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C5Me5)(2)Th[kappa(2)-(C,C')-(CH2)(CH2)PPh2]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH3PPh3]X, X = Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene.
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