Infrared Spectra of CH3-MH through Methane Activation by Laser-Ablated Sn, Pb, Sb, and Bi Atoms
Infrared Spectra of CH3-MH through Methane Activation by Laser-Ablated Sn, Pb, Sb, and Bi Atoms
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DOI：
10.1021/jp305117d
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发表时间：
2012-08-23
影响因子：
2.9
通讯作者：
Andrews, Lester
中科院分区：
文献类型：
--
作者：
Cho, Han-Gook;Andrews, Lester
用激光烧蚀Sn、Pb、Sb和Bi原子进行了甲烷活化。所有四种金属都产生插入配合物（CH3-MH），但随后的h从C向M迁移，形成CH2-MH2和CH-MH3配合物，没有观察到。我们以前和现在的实验和计算结果表明，随着14和15族原子质量的增加，高氧化态配合物变得不那么受欢迎，这与过渡金属的一般趋势相反。在样品缩合反应过程中，碳-氢键明显插入，反应后产物在宽带光解中解离。与许多过渡金属类似物不同，插入配合物含有近直角的C-M- h部分，因为金属中心对C-M和M-H键的p贡献很大。计算出的这些主要金属族的亚甲基结构并不准确，可能是因为缺少价d轨道。
Methane activation has been carried out by laser-ablated Sn, Pb, Sb, and Bi atoms. All four metals generate the insertion complex (CH3-MH), but subsequent H-migration from C to M to form CH2-MH2 and CH-MH3 complexes is not observed. Our previous and present experimental and computational results indicate that the higher oxidation state Complexes become less favored with increasing atomic mass in groups 14 and 15, which is opposite the general trend found for transition metals. The C-H bond insertion evidently occurs during reaction on sample condensation, and the product dissociates on broad-band photolysis afterward. The insertion complex contains a near right angle C-M-H moiety because of high p contribution from the metal center to the C-M and M-H bonds unlike many transition-metal analogues. The computed methylidene structures for these main group metals are not agostic possibly because of the absence of valence d-orbitals.