Infrared Spectra of CH3-MF and Several Fragments Prepared by Methyl Fluoride Reactions with Laser-Ablated Cu, Ag, and Au Atoms
Infrared Spectra of CH3-MF and Several Fragments Prepared by Methyl Fluoride Reactions with Laser-Ablated Cu, Ag, and Au Atoms
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DOI：
10.1021/ic2013842
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发表时间：
2011-10-17
影响因子：
4.6
通讯作者：
Andrews, Lester
中科院分区：
文献类型：
--
作者：
Cho, Han-Gook;Andrews, Lester
已经进行了激光烧蚀的激发的第11族金属原子与CH 3F同位素异构体的反应，导致除了用于金的较小络合物之外，用于Cu、Ag和Au的CH 3-MY和CH 2F-M络合物的产生。红外光谱中的产物根据其频率、同位素位移以及与DFT计算的频率的相关性来鉴定，表明钴金属的M-F插入和H原子的释放容易发生。CH 3-AuF的相对低的解离能，得到几个较小的Au配合物与这些片段的观察是一致的。CF-AuH和CH_2-AuF的C-Au键表现出相当大的π特征，而亚甲基CH_2-AuF含有一个真正的双键。相比之下，CH 2-Au和CH 2-AuH的键级较低，表明键合到Au的F收缩金5d轨道，以便与π键合的碳2 p轨道更好地重叠。
Reactions of laser-ablated, excited group 11 metal atoms with CH3F isotopomers have been carried out, leading to the generation of CH3-MY and CH2F-M complexes for Cu, Ag, and Au in addition to smaller complexes for gold. The products in the infrared spectra identified on the basis of their frequencies, isotopic shifts, and correlation with DFT calculated frequencies reveal that M-F insertion by the coinage metals and H atom release readily occur. The relatively low dissociation energies of CH3-AuF to give several smaller Au complexes are consistent with the observation of these fragments. The C-Au bonds of CF-AuH and CH2-AuF exhibit considerable pi character, and the methylidene CH2-AuF contains a true double bond. In contrast, the bond orders of CH2-Au and CH2-AuH are lower, indicating that F bonded to Au contracts the gold 5d orbitals for better overlap with the carbon 2p orbital for pi bonding.