Department of Chemistry, University of Incheon, 12-1 Songdo-dong, Yonsu-gu, Incheon, 406-772, South Korea.
Dalton Trans. 2011 Nov 14;40(42):11115-24. doi: 10.1039/c0dt01827a. Epub 2011 Mar 30.
Methane activation by laser-ablated, excited Group 11 metal atoms has been carried out, leading to generation of CH(3)-MH, CH(3)-M, and CH(3)-MH(-), which are identified in the product infrared spectra on the basis of isotopic shifts and correlation with DFT calculated frequencies. The products reveal that C-H insertion by excited Au, Ag, and Cu readily occurs, and subsequent hydride-detachment or electron addition also follows. Each type of product has similar photochemical properties regardless of the metal. DFT computed energies reveal facile hydride dissociation and high electron affinities for the insertion complexes. The methyl metal species have the shortest C-M bonds, consistent with their highest calculated effective bond order, and the CH(3)-MH complexes have higher electron affinities than the metal atoms.
用激光烧蚀激发的 Group 11 金属原子对甲烷进行了激活，生成了 CH(3)-MH、CH(3)-M 和 CH(3)-MH(-)，这些物质在产物的红外光谱中通过同位素位移和与 DFT 计算频率的关联被识别出来。研究结果表明，受激 Au、Ag 和 Cu 很容易发生 C-H 插入，随后发生氢化物的脱离或电子加成。无论金属如何，每种类型的产物都具有相似的光化学性质。DFT 计算的能量表明插入配合物的氢化物容易解离且具有高电子亲合能。甲基金属物种的 C-M 键最短，与其最高的计算有效键序一致，并且 CH(3)-MH 配合物的电子亲合能高于金属原子。
