New insights into solvolysis and reorganization energy from gas-phase, electrochemical, and theoretical studies of oxo-Tp*Mo(V) molecules.
New insights into solvolysis and reorganization energy from gas-phase, electrochemical, and theoretical studies of oxo-Tp*Mo(V) molecules.
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DOI：
10.1021/ic9011058
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发表时间：
2009-09-21
影响因子：
4.6
通讯作者：
Enemark, John H.
中科院分区：
文献类型：
--
作者：
Vannucci, Aaron K.;Snyder, Rae Ana;Gruhn, Nadine E.;Lichtenberger, Dennis L.;Enemark, John H.
研究了通式为Tp*MoO(OR)₂的分子（其中Tp* = 氢三（3,5 - 二甲基 - 1 - 吡唑基）硼酸盐，对于醇盐配体(OR)₂ = (OMe)₂、(OEt)₂和(OnPr)₂，对于二醇配体(OR)₂ = O(CH₂)₃O、O(CH₂)₄O和O[CH(CH₃)CH₂CH(CH₃)]O），采用气相光电子能谱、循环伏安法和密度泛函理论计算来研究配体尺寸和结构增加对氧钼核的影响。氧化电位和第一电离能显示对二醇配体和醇盐配体的特性敏感。溶液相氧化电位和气相电离能之间的线性相关性导致了一个大于1的意外斜率。密度泛函理论计算表明，这个氧化电位比垂直电离能对取代更敏感的体系的独特例子是由于阳离子重组能的巨大差异，对于具有二醇配体的分子，其阳离子重组能为0.2 eV或更小，而对于具有醇盐配体的分子则约为0.5 eV。
Molecules of the general form Tp*MoO(OR)2 (where Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate and (OR)2 = (OMe)2, (OEt)2, and (OnPr)2 for alkoxide ligands, and (OR)2 = O(CH2)3O, O(CH2)4O, and O[CH(CH3)CH2CH(CH3)]O for diolato ligands) were studied using gas-phase photoelectron spectroscopy, cyclic voltammetry, and density functional theory calculations to examine the effect of increasing ligand size and structure on the oxo-molybdenum core. Oxidation potentials and first ionization energies are shown to be sensitive to the character of the diolato and alkoxide ligands. A linear correlation between the solution-phase oxidation potentials and the gas-phase ionization energies resulted in an unexpected slope of greater than unity. Density functional theory calculations indicated that this unique example of a system in which oxidation potentials are more sensitive to substitution than vertical ionization energies is due to the large differences in the cation reorganization energies, which range from 0.2 eV or less for the molecules with diolato ligands to around 0.5 eV for the molecules with alkoxide ligands.
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影响因子：
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作者：
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