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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Molecular motions in a fluxional (eta(6)-indenyl) tricarbonylchromium hemichelate: a density functional theory molecular dynamics study
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Molecular motions in a fluxional (eta(6)-indenyl) tricarbonylchromium hemichelate: a density functional theory molecular dynamics study

机译：孔隙中的分子运动（ETA（6） - 吲烯基）三羰基溴化碳：密度泛函理论分子动力学研究

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摘要

A comprehensive Density Functional Theory (DFT) study is reported on molecular motions occurring in a hemichelate complex, formally composed of the (eta(3)-2-methylallyl)Pd(II) cation bonded to a (eta(6)-indenyl) tricarbonylchromium anion, that has been recognized as being highly fluxional in a previous experimental study (C. Werle, M. Hamdaoui, C. Bailly, X.-F. Le Goff, L. Brelot and J.-P. Djukic, J. Am. Chem. Soc., 2013, 135, 1715-1718). Its dynamics can be decomposed into three molecular motions: (i) the indenyl ligand can switch from a eta(1) to a eta(3) binding mode to Pd, (ii) the Cr(CO)(3) moiety forms loose interactions with Pd, and can potentially rotate around the aryl-Cr axis, and (iii) the binding mode of the 2-methylallyl ligand to Pd may undergo partial decoordination or rotation around the Pd-C axis. Herein, DFT based molecular dynamics simulations have been performed to provide microscopic insights into the dynamical behaviour of the complex on a 100 ps timescale. QTAIM analyses have been performed over trajectories to investigate the rearrangement of its electronic structure over time. Next, free energy calculations, following the metadynamics approach, have been undertaken to compute thermodynamic and kinetic data relative to the molecular rearrangements occurring in the complex. The results show that the fastest motion is the ring slippage of the indenyl ligand, and that this motion is coupled with the rotation of the 2-methylallyl ligand. Conversely, the Cr(CO)(3) rotation is significantly slower, however, a fast rocking motion is observed, consisting of transient approaches of carbonyl ligands to Pd. QTAIM analyses point to loose Pd/carbonyl and Pd/Cr interactions on average, that significantly evolve over time as fluxional motions occur.
机译：报告了综合密度函数理论（DFT）研究关于在半核复合物中发生的分子运动，用（ETA（3）-2-甲基aly1）Pd（II）键合至A（ETA（6） - 茚基）三羰基溴阴离子，已被认为是先前实验研究中的高度股份（C. hamdaoui，C.Bailly，X.-f.Le Goff，L.Brot和J.-P. Djukic，J. am。化学。Soc。，2013,135,1715-1718）。其动力学可以分解成三种分子运动：（I）茚基配体可以从ETA（1）切换到ETA（3）结合模式至Pd，（II）Cr（CO）（3）部分形成松散的相互作用具有PD，并且可以围绕芳基-Cr轴旋转，并且（iii）2-甲基alallyl配体与Pd的结合模式可以围绕PD-C轴进行部分解构或旋转。这里，已经进行了基于DFT的分子动力学模拟，以在100ps时间尺度上提供对复合物的动态行为的微观洞察。已经通过轨迹进行了Qtaim分析，以调查其电子结构随时间的重新排列。接下来，已经进行了在元动力学方法之后的自由能量计算，以计算相对于复合物中发生的分子重排的热力学和动力学数据。结果表明，最快运动是茚基配体的环形滑动，并且该运动与2-甲基alyl配体的旋转耦合。相反，Cr（CO）（3）旋转显着较慢，但是，观察到快速摇摆运动，由羰基配体的瞬时接近PD。 Qtai毒分析点为松散的Pd /羰基和PD / Cr平均相互作用，随着群体运动而显着发展。

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