Influence of substituents on the nature of metal⋯π interaction and its cooperativity with halogen bond
- The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005 (China)
High-level quantum chemical calculations have been performed to investigate the influence of substituents on the metal—π interaction and its cooperative effect with halogen bond in C{sub 2}X{sub 4}⋯MCN⋯ClF (X = H, CN, CH{sub 3}; M = Cu, Ag, Au). The strong electron-withdrawing group CN weakens the metal—π covalent interaction, while the weak electron-withdrawing group CH{sub 3} strengthens it. The metal—π covalent interaction is dominated by electrostatic energy although the AuCN complex has approximately equal electrostatic and polarization contributions. However, the metal—π covalent interaction is governed by polarization energy due to the CN substitution. A cooperative effect is found for the halogen bond and metal—π interactions in C{sub 2}H{sub 4}⋯MCN⋯ClF, while a diminutive effect occurs in the triads by the CN substituent. Orbital interaction analysis indicates that the strong electron-withdrawing group CN causes the C=C group vary from a stronger donor orbital to a stronger acceptor orbital.
- OSTI ID:
- 22493491
- Journal Information:
- Journal of Chemical Physics, Vol. 143, Issue 5; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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