二氟化氪配位化合物的一个罕见例子：[BrOF2][AsF6]·2KrF2,Journal of the American Chemical Society

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二氟化氪配位化合物的一个罕见例子：[BrOF2][AsF6]·2KrF2
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2010-03-17 , DOI: 10.1021/ja9098559
David S. Brock ₁ , Jonathan J. Casalis de Pury ₁ , Hélène P. A. Mercier ₁ , Gary J. Schrobilgen ₁ , Bernard Silvi ₁

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本研究描述了 [BrOF(2)][AsF(6)] x 2 KrF(2) 的合成、其结构特征和键合。虽然以前曾报道过几个具有过渡金属中心的 KrF(2) 加合物，但没有一个被晶体学表征。[BrOF(2)][AsF(6)] x 2 KrF(2) 的固态拉曼光谱已在量子化学计算的帮助下分配。[BrOF(2)][AsF(6)] x 2 KrF(2) 的低温 (-173 摄氏度) X 射线晶体结构由孤立的分子单元组成，代表了 KrF(2) 与一个主族原子。BrOF(2)(+) 阳离子周围的配位几何使自由价电子孤对比在自由 BrOF(2)(+) 中更紧凑。KrF(2) 配体被协调到 BrOF(2)(+) 的氟原子与 AsF(6)(-) 阴离子协调反式到氧。已经进行了分子中原子的量子理论 (QTAIM) 和电子局域化函数 (ELF) 分析，以定义复合物中键合的性质。大量电荷 (0.25 e) 从两个 KrF(2) 配体（每个配体 0.10 e）和 AsF(6)(-) 阴离子 (0.05 e) 转移到 BrOF(2)(+)。KrF(2) 配体中也会发生明显的极化，这增强了氟桥的阴离子特性。相互作用能主要由带正电的溴原子与周围氟原子的静电相互作用控制。25 e) 从两个 KrF(2) 配体（每个 0.10 e）和 AsF(6)(-) 阴离子（0.05 e）转移到 BrOF(2)(+)。KrF(2) 配体中也会发生明显的极化，这增强了氟桥的阴离子特性。相互作用能主要由带正电的溴原子与周围氟原子的静电相互作用控制。25 e) 从两个 KrF(2) 配体（每个 0.10 e）和 AsF(6)(-) 阴离子（0.05 e）转移到 BrOF(2)(+)。KrF(2) 配体中也会发生明显的极化，这增强了氟桥的阴离子特性。相互作用能主要由带正电的溴原子与周围氟原子的静电相互作用控制。

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A Rare Example of a Krypton Difluoride Coordination Compound: [BrOF2][AsF6]·2KrF2

The synthesis of [BrOF(2)][AsF(6)] x 2 KrF(2), its structural characterization, and bonding are described in this study. Although several KrF(2) adducts with transition metal centers have been previously reported, none have been crystallographically characterized. The solid-state Raman spectrum of [BrOF(2)][AsF(6)] x 2 KrF(2) has been assigned with the aid of quantum-chemical calculations. The low-temperature (-173 degrees C) X-ray crystal structure of [BrOF(2)][AsF(6)] x 2 KrF(2) consists of isolated molecular units and represents an example of KrF(2) coordinated to a main-group atom. The coordination geometry around the BrOF(2)(+) cation renders the free valence electron lone pair more compact than in free BrOF(2)(+). The KrF(2) ligands are coordinated trans to the fluorine atoms of BrOF(2)(+) with the AsF(6)(-) anion coordinated trans to oxygen. The quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF) analyses have been carried out in order to define the nature of the bonding in the complex. A significant amount of charge (0.25 e) is transferred to BrOF(2)(+) from the two KrF(2) ligands (0.10 e each) and from the AsF(6)(-) anion (0.05 e). Significant polarization also occurs within the KrF(2) ligands, which enhances the anionic characters of the fluorine bridges. The interaction energy is mostly governed by the electrostatic interaction of the positively charged bromine atom with the surrounding fluorine atoms.

更新日期：2010-03-17

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