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Coinage-Metal Bond between [1.1.1]Propellane and M(2)/MCl/MCH(3) (M = Cu, Ag, and Au): Cooperativity and Substituents
A coinage-metal bond has been predicted and characterized in the complexes of [1.1.1]propellane (P) and M(2)/MCl/MCH(3) (M = Cu, Ag, and Au). The interaction energy varies between −16 and −47 kcal/mol, indicating that the bridgehead carbon atom of P has a good affinity for the coinage atom. The coin...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6680963/ https://www.ncbi.nlm.nih.gov/pubmed/31319542 http://dx.doi.org/10.3390/molecules24142601 |
Sumario: | A coinage-metal bond has been predicted and characterized in the complexes of [1.1.1]propellane (P) and M(2)/MCl/MCH(3) (M = Cu, Ag, and Au). The interaction energy varies between −16 and −47 kcal/mol, indicating that the bridgehead carbon atom of P has a good affinity for the coinage atom. The coinage-metal bond becomes stronger in the Ag < Cu < Au sequence. Relative to M(2), both MCl and MCH(3) engage in a stronger coinage-metal bond, both -Cl and -CH(3) groups showing an electron-withdrawing property. The formation of coinage-metal bonding is mainly attributed to the donation orbital interactions from the occupied C-C orbital into the empty metal orbitals and a back-donation from the occupied d orbital of metal into the empty C-C anti-bonding orbital. In most complexes, the coinage-metal bond is dominated by electrostatic interaction, with moderate contribution of polarization. When P binds simultaneously with two coinage donors, negative cooperativity is found. Moreover, this cooperativity is prominent for the stronger coinage-metal bond. |
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