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Issue 12, 2015
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Role of the cation formal charge in cation–π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations

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Abstract

The role of the metal formal charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η222-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.

Graphical abstract: Role of the cation formal charge in cation–π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations

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Article information


Submitted
06 Sep 2015
Accepted
15 Oct 2015
First published
19 Oct 2015

New J. Chem., 2015,39, 9963-9968
Article type
Paper

Role of the cation formal charge in cation–π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations

A. O. Ortolan, G. F. Caramori, G. Frenking and A. Muñoz-Castro, New J. Chem., 2015, 39, 9963
DOI: 10.1039/C5NJ02384J

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