Vellé Alba, Rodríguez-Santiago Luis, Sodupe Mariona, Sanz Miguel Pablo J
Departamento de Química Inorgánica, Instituto de Síntesis QuímicayCatálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC, 50009, Zaragoza, Spain.
Departament de Química, Universitat Autònoma de Barcelona, 08193, Bellaterra, Barcelona, Spain.
Chemistry. 2020 Jan 22;26(5):997-1002. doi: 10.1002/chem.201904507. Epub 2020 Jan 9.
Metallophilicity is an essential concept that builds upon the attraction between closed shell metal ions. We report on the [M (bisNHC) ] (M=Au , Ag ; NHC=N-heterocyclic carbene) systems, which display almost identical features in the solid state. However, in solution the Au cation exhibits a significantly higher degree of rigidity owed to the stronger character of the aurophilic interactions. Both Au and Ag cationic constructs are able to accommodate Ag ions via M-M interactions, despite their inherent Coulombic repulsion. When electrostatic repulsion between host and guest is partially diminished, M-M distances are substantially shortened. Quantum chemical calculations estimate intermetallic bond orders up to 0.2. Although at the limit of (or beyond) the van der Waals radii, metallophilic interactions are responsible for their behavior in solution.
金属亲合性是一个基于闭壳层金属离子间吸引力的重要概念。我们报道了[M (双NHC)]（M = Au、Ag；NHC = N - 杂环卡宾）体系，该体系在固态时表现出几乎相同的特征。然而，在溶液中，由于金亲合相互作用更强，金阳离子表现出显著更高的刚性程度。尽管存在固有的库仑排斥力，但Au和Ag阳离子结构都能够通过M - M相互作用容纳Ag离子。当主体与客体之间的静电排斥力部分减弱时，M - M距离会大幅缩短。量子化学计算估计金属间键级高达0.2。尽管处于范德华半径的极限（或超过该极限），金属亲合相互作用决定了它们在溶液中的行为。
