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首页> 外文期刊>Organometallics >Silyl substitution effects on metal-pentadienyl bonding: Synthesis, structure, photoelectron spectroscopy, and electronic structure of a high-valent half-open zirconocene
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Silyl substitution effects on metal-pentadienyl bonding: Synthesis, structure, photoelectron spectroscopy, and electronic structure of a high-valent half-open zirconocene

机译：甲硅烷基取代基对金属-戊二烯基键合的影响：高价半开放式茂锆的合成，结构，光电子能谱和电子结构

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摘要

The molecule Cp(3-Me3Si-6,6-dmch)ZrI2 (Cp = eta(5)-cyclopentadienyl; 3-Me3Si-6,6-dmch = eta(5)-3-trimethylsilyl-6,6-dimethylcyclohexadienyl) has been synthesized, and the molecular and electronic structures have been investigated. Photoelectron spectroscopy shows that substitution of a trimethylsilyl group in place of a hydrogen atom on the 6,6-dmch ligand destabilizes all of the ionizations of Cp(3-Me3Si-6,6-dmch)ZrI2 by ca. 0.1-0.2 eV compared to those of Cp(6,6-dmch)ZrI2. Density functional calculations accurately reproduce the experimental structure of the molecule and agree with the observed shift of all ionizations to lower energies. Interestingly, the ionizations are calculated to shift to lower energies without the expected increase in electron density at the metal center. This apparent contradiction is understood from analysis of one-center and two-center charge effects in the molecule. As a consequence of these charge effects, the silyl substitution makes the 3-Me3Si-6,6-dmch ligand a slightly better donor and, surprisingly, also a better acceptor ligand than the 6,6-dmch ligand.
机译：分子Cp（3-Me3Si-6,6-dmch）ZrI2（Cp = eta（5）-环戊二烯基; 3-Me3Si-6,6-dmch = eta（5）-3-三甲基甲硅烷基-6,6-二甲基环己二烯基已合成，并研究了分子和电子结构。光电子能谱表明，用三甲基甲硅烷基取代6,6-dmch配体上的氢原子可使Cp（3-Me3Si-6,6-dmch）ZrI2的所有电离稳定约3.7％。与Cp（6,6-dmch）ZrI2相比，为0.1-0.2 eV。密度泛函计算准确地再现了分子的实验结构，并与观察到的所有电离向较低能量的移动一致。有趣的是，电离被计算为转移到较低的能量，而金属中心的电子密度没有预期的增加。通过分析分子中的一个中心和两个中心的电荷效应可以理解这种明显的矛盾。由于这些电荷效应，甲硅烷基取代使得3-Me3Si-6,6-dmch配体比6,6-dmch配体略好一些，而且令人惊讶地，它也是一个更好的受体配体。

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