Relevance of Orbital Interactions and Pauli Repulsion in the Metal-Metal Bond of Coinage Metals.
Relevance of Orbital Interactions and Pauli Repulsion in the Metal-Metal Bond of Coinage Metals.
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DOI：
10.1021/acs.inorgchem.7b02994
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发表时间：
2018-03-05
影响因子：
4.6
通讯作者：
Guerra CF
中科院分区：
文献类型：
--
作者：
Brands MB;Nitsch J;Guerra CF
相对性和分散性在亲金属性中的重要性已经在许多研究中讨论过。也有人推测在闭合壳层d10-d10金属原子之间的键合中存在杂化，但是在金属-金属键中存在吸引MO相互作用仍然是一个正在进行的争论。本文对原子二聚体（M+···M+）和分子垂直配体[H3 P-M-X]2（M = Cu，Ag，Au; X = F，Cl，Br，I）中的亲金属相互作用进行了定量的分子轨道分析和能量分解。我们的计算研究证明，除了普遍接受的色散相互作用，轨道相互作用和泡利排斥也发挥了至关重要的作用，金属-金属键的强度和长度。虽然对于M+···M+，轨道相互作用大于泡利排斥，导致净吸引MO相互作用，但垂直[H3 P-M-X]二聚体中的成键机制不同，因为供体和受体轨道之间的距离较大。因此，泡利排斥要大得多，并且两轨道，四电子排斥占主导地位。吸引和排斥：我们对原子二聚体（M+···M+）和分子垂直结构[H3 P-M-X]2（其中M = Cu，Ag，Au; X = F，Cl，Br，I）中亲金属相互作用的计算研究证明，除了普遍接受的色散相互作用外，吸引和排斥MO相互作用在亲金属性中起着至关重要的作用。
The importance of relativity and dispersion in metallophilicity has been discussed in numerous studies. The existence of hybridization in the bonding between closed shell d10–d10 metal atoms has also been speculated, but the presence of attractive MO interaction in the metal–metal bond is still a matter of an ongoing debate. In this comparative study, a quantitative molecular orbital analysis and energy decomposition is carried out on the metallophilic interaction in atomic dimers (M+···M+) and molecular perpendicular [H3P–M–X]2 (where M = Cu, Ag, and Au; X = F, Cl, Br, and I). Our computational studies prove that besides the commonly accepted dispersive interactions, orbital interactions and Pauli repulsion also play a crucial role in the strength and length of the metal–metal bond. Although for M+···M+ the orbital interaction is larger than the Pauli repulsion, leading to a net attractive MO interaction, the bonding mechanism in perpendicular [H3P–M–X] dimers is different due to the larger separation between the donor and acceptor orbitals. Thus, Pauli repulsion is much larger, and two-orbital, four-electron repulsion is dominant. Attract and repel: Our computational studies on the metallophilic interaction in atomic dimers (M+···M+) and molecular perpendicular [H3P−M−X]2 (where M = Cu, Ag, and Au; X = F, Cl, Br, and I) prove that besides the commonly accepted dispersive interactions attractive and repulsive MO interactions play a crucial role in metallophilicity.
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