Photoelectron spectroscopy and DFT calculations of easily ionized quadruply bonded Mo2(4+) compounds and their bicyclic guanidinate precursors.
Photoelectron spectroscopy and DFT calculations of easily ionized quadruply bonded Mo2(4+) compounds and their bicyclic guanidinate precursors.
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易电离四键 Mo2(4) 化合物及其双环胍酸盐前体的光电子能谱和 DFT 计算。
DOI：
10.1021/jp061820m
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
C. Wilkinson
中科院分区：
文献类型：
--
作者：
F. Cotton;Jason C. Durivage;N. Gruhn;D. Lichtenberger;C. A. Murillo;Laura O Van Dorn;C. Wilkinson
光电子能谱显示一系列含有五元环和六元环以及取代烷基的各种组合的五种双环胍化合物很容易电离，其中具有两个六元环和四个乙基的化合物最容易电离。相应的阴离子能够形成具有四键Mo2(4+)单元的叶轮化合物，该化合物也易于电离。最容易电离的化合物是乙基取代的 Mo2(TEhpp)4 络合物，它具有以 4.27 +/- 0.03 eV 为中心的宽第一电离带，并且在 3.93 +/- 0.03 eV 的极低能量处开始电离。即使是配体含有两个五元环的化合物，由于配体咬合力大，有利于长Mo-Mo分离，其电离能(4.78 eV)也低于众所周知的有机金属还原剂，如(eta5-C9Me7)2Co和(eta5-C5Me5)2Cr。
A series of five bicyclic guanidinate compounds containing various combinations of five- and six-membered rings and substituted alkyl groups have been shown by photoelectron spectroscopy to be easily ionized, with the one having two six-membered rings and four ethyl groups being the most easily ionized. The corresponding anions are capable of forming paddlewheel compounds having quadruply bonded Mo2(4+) units which are also easy to ionize. The most easily ionized compound is the ethyl-substituted Mo2(TEhpp)4 complex which has a broad first ionization band centered around 4.27 +/- 0.03 eV and an ionization onset at the very low energy of 3.93 +/- 0.03 eV. Even the compound with ligands containing two five-membered rings, which favors a long Mo-Mo separation because of the large ligand bite, has an ionization energy (4.78 eV) that is less than those of well-known organometallic reducing agents such as (eta5-C9Me7)2Co and (eta5-C5Me5)2Cr.