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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical study of complexes of extended cyclopentadienyl ligands with zinc and cadmium
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Theoretical study of complexes of extended cyclopentadienyl ligands with zinc and cadmium

机译：扩展的环戊二烯基配体与锌和镉的配合物的理论研究

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Using density functional theory, we have theoretically studied various kinds of complexes of cyclopentadienyl and dicyclopentadienyl ligands with zinc and cadmium atoms of oxidation state +1. We first find that a sandwich complex Cp*-Zn-Zn-Cp* that was recently identified by Resta et al, (Science 2004, 305, 1136) has a large overall binding energy (=-3.19 eV), where Cp* denotes the pentamethyl cyclopentadienyl group. In addition, Cp-Zn-Zn-Cp is found to have a binding energy even larger by 0.93 eV, where Cp is a cyclopentadienyl ligand without methyl groups attached. Electronic structure analysis shows accumulation of electron density between Zn atoms, confirming the existence of Zn-Zn bond that is as strong as typical transition metal-halide bonds. In addition, our calculation suggests the possible existence of similar complexes Cp*-Zn-Cd-Cp* and Cp-Zn-Cd-Cp with a Zn-Cd bond not known thus far. Furthermore, study on the dimetallic complexes of dicyclopentadienyl ligands also predicts results which hold potential application to organometallic chemistry and organic synthesis: (a) Complexes involving a stiff ligand Dp can presumably exist in the form of dimerized sandwich complexes Dp-2M(1)-2M(2)-Dp (M-1, M-2 = Zn, Cd) with two metalmetal bonds. Their overall binding energies amount to -1.84 to -3.48 eV depending upon the kinds of metallic atoms, the strongest binding corresponding to dizinc complex. (b) Complexes involving more flexible ligand Ep can also form similar sandwich complexes Ep-2M(1) -2M(2)-Ep, but with much larger overall binding energies (=-4.97 to -7.09 eV). In addition, they can also exist in the form of nonsandwich complexes M-1-Ep-M-2 involving only one ligand. Unlike most of dimetallic complexes of other transition metals, syn conformations are found to be exceptionally stable due to the formation of M-1-M-2 bonds. Careful electronic structure analysis gives deep insight into the nature of observed phenomena.
机译：使用密度泛函理论，我们从理论上研究了环戊二烯基和二环戊二烯基配体与氧化态为+1的锌和镉原子的各种配合物。我们首先发现，最近由Resta等人发现的三明治复合物Cp * -Zn-Zn-Cp *（Science 2004，305，1136）具有较大的整体结合能（= -3.19 eV），其中Cp *表示五甲基环戊二烯基。另外，发现Cp-Zn-Zn-Cp具有甚至更大的0.93eV的结合能，其中Cp是没有连接甲基的环戊二烯基配体。电子结构分析显示Zn原子之间电子密度的积累，从而证实了Zn-Zn键的强度与典型的过渡金属卤化物键一样强。另外，我们的计算表明可能存在类似的配合物Cp * -Zn-Cd-Cp *和具有Zn-Cd键的Cp-Zn-Cd-Cp的存在，目前尚不清楚。此外，对二环戊二烯基配体的双金属配合物的研究也预测了可能在有机金属化学和有机合成中应用的结果：（a）涉及刚性配体Dp的配合物可能以二聚夹心配合物Dp-2M（1）-的形式存在-具有两个金属键的2M（2）-Dp（M-1，M-2 = Zn，Cd）。它们的总结合能取决于金属原子的种类，为-1.84至-3.48 eV，最强的结合力对应于二锌配合物。 （b）包含更灵活的配体Ep的复合物也可以形成类似的三明治复合物Ep-2M（1）-2M（2）-Ep，但具有更大的整体结合能（= -4.97至-7.09 eV）。另外，它们还可以以仅包含一个配体的非夹心复合物M-1-Ep-M-2的形式存在。与大多数其他过渡金属的双金属配合物不同，由于形成了M-1-M-2键，顺式构象异常稳定。仔细的电子结构分析可深入了解观察到的现象的性质。

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