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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Electronic states and metal-ligand bonding of gadolinium complexes of benzene and cyclooctatetraene
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Electronic states and metal-ligand bonding of gadolinium complexes of benzene and cyclooctatetraene

机译：苯与环辛酸酯的of配合物的电子态和金属配体键合

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摘要

Gadolinium (Gd) complexes of benzene (C _6H_ 6) and (1,3,5,7-cyclooctatetraene) (C _8H _8) were produced in a laser-vaporization supersonic molecular beam source and studied by single-photon pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy. Adiabatic ionization energies and metal-ligand stretching frequencies were measured for the first time from the ZEKE spectra. Metal-ligand bonding and electronic states of the neutral and cationic complexes were analyzed by combining the spectroscopic measurements with ab initio calculations. The ground states of Gd(C _6H _6) and [Gd(C _6H _6)] ~+ were determined as ~(11)A _2 and ~(10)A_ 2, respectively, with C _(6v) molecular symmetry. The ground states of Gd(C _8H_ 8) and [Gd(C_ 8H_ 8)] + were identified as ~9A _2 and~8A _2, respectively, with C _(8v) molecular symmetry. Although the metal-ligand bonding in Gd(C _6H _6) is dominated by the covalent interaction, the bonding in Gd(C_ 8H _8) is largely electrostatic. The bonding in the benzene complex is much weaker than that in the cyclooctatetraene species. The strong bonding in Gd(C _8H _8) arises from two-electron transfer from Gd to C _8H _8, which creates a strong charge-charge interaction and converts the tub-shaped ligand into a planar form. In both systems, Gd 4f orbitals are localized and play little role in the bonding, but they contribute to the high electron spin multiplicities.
机译：苯（C _6H_ 6）和（1,3,5,7-环辛酸酯）（C _8H _8）的配合物是在激光汽化超声分子束源中产生的，并通过单光子脉冲场电离研究零电子动能（ZEKE）光谱。绝热电离能和金属配体的拉伸频率是从ZEKE谱图中首次测量的。通过结合光谱测量和从头算来分析中性和阳离子配合物的金属-配体键和电子态。 Gd（C _6H _6）和[Gd（C _6H _6）]〜+的基态分别确定为〜（11）A _2和〜（10）A_2，具有C _（6v）分子对称性。具有C _（8v）分子对称性的Gd（C _8H_ 8）和[Gd（C_8H_ 8）] +的基态分别确定为〜9A _2和〜8A _2。尽管Gd（C _6H _6）中的金属-配体键主要由共价键相互作用，但Gd（C_8H _8）中的键主要是静电的。苯络合物中的键合比环辛酸酯中的键合弱得多。 Gd（C _8H _8）中的强键是从Gd到C _8H _8的两电子转移而产生的，这产生了很强的电荷-电荷相互作用并将桶形配体转化为平面形式。在这两个系统中，Gd 4f轨道都是局部的，在键合中几乎没有作用，但它们有助于高电子自旋多重性。

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