Metal Centers as Nucleophiles: Oxymoron of Halogen Bond-Involving Crystal Engineering |
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| Authors: | Dr. Daniil M. Ivanov Prof. Dr. Nadezhda A. Bokach Prof. Dr. Vadim Yu. Kukushkin Prof. Dr. Antonio Frontera |
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| Affiliation: | 1. Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg, 199034 Russian Federation;2. Department of Chemistry, Universitat de les Illes Balears, Palma de Mallorca Baleares, 07122 Spain |
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| Abstract: | This review highlights recent studies discovering unconventional halogen bonding (HaB) that involves positively charged metal centers. These centers provide their filled d-orbitals for HaB, and thus behave as nucleophilic components toward the noncovalent interaction. This role of some electron-rich transition metal centers can be considered an oxymoron in the sense that the metal is, in most cases, formally cationic; consequently, its electron donor function is unexpected. The importance of Ha⋅⋅⋅d-[M] (Ha=halogen; M is Group 9 (Rh, Ir), 10 (Ni, Pd, Pt), or 11 (Cu, Au)) interactions in crystal engineering is emphasized by showing remarkable examples (reported and uncovered by our processing of the Cambridge Structural Database), where this Ha⋅⋅⋅d-[M] directional interaction guides the formation of solid supramolecular assemblies of different dimensionalities. |
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| Keywords: | halogen bonding noncovalent interactions nucleophilic metal centers σ-hole interactions theoretical calculations |
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