Cho Han-Gook, Andrews Lester
Department of Chemistry, University of Incheon, 177 Dohwa-dong, Nam-ku, Incheon, 402-749, South Korea.
Inorg Chem. 2008 Mar 3;47(5):1653-62. doi: 10.1021/ic701505w. Epub 2008 Feb 8.
Rhenium carbyne complexes (HC identical with ReH 3, HC identical with ReH 2X, HC identical with ReHX 2, [X = F, Cl, and Br] and CH 3C identical with ReH 3) are produced by reactions of laser-ablated Re atoms with methane, methyl halides, methylene halides, and ethane via oxidative C-H(X) insertion and alpha-hydrogen migration in favor of the carbon-metal triple bond. The stabilities of the carbyne complexes relative to other possible products are predicted by DFT calculations. The diagnostic methylidyne C-H stretching absorptions of HC identical with ReH 3 and its mono- and dihalo derivatives are observed on the blue sides of the precursor C-H stretching bands, and the frequency decreases and the bond length increases in the order of H, F, Cl, and Br, following the decreasing s character in hybridization for the C-H bond. The dihalo methylidynes have higher C-H stretching frequencies and s characters than the monohalo species. The rhenium methylidynes have C s structures, and as a result the HC identical with ReH 3 and CH 3C identical with ReH 3 complexes have two equivalent shorter and one longer Re-H bonds, as compared to the tungsten methylidyne HC identical with WH 3 with three equivalent W-H bonds.
铼卡宾配合物（HC≡ReH₃、HC≡ReH₂X、HC≡ReHX₂，[X = F、Cl和Br]以及CH₃C≡ReH₃）是通过激光烧蚀的Re原子与甲烷、卤代甲烷、二卤代甲烷和乙烷反应，经由氧化C-H(X)插入和α-氢迁移而生成的，有利于形成碳-金属三键。通过密度泛函理论计算预测了卡宾配合物相对于其他可能产物的稳定性。在HC≡ReH₃及其单卤代和二卤代衍生物的前驱体C-H伸缩带的蓝侧观察到了诊断性的亚甲基C-H伸缩吸收，并且频率按照H、F、Cl和Br的顺序降低，键长增加，这是由于C-H键杂化中s成分的减少。二卤代亚甲基比单卤代物种具有更高的C-H伸缩频率和s成分。铼亚甲基具有Cₛ结构，因此与具有三个等效W-H键的钨亚甲基HC≡WH₃相比，HC≡ReH₃和CH₃C≡ReH₃配合物具有两个等效的较短和一个较长的Re-H键。
