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

Ortolan A.O.; Caramori G.F.; Frenking G.; Muñoz-Castro A.

dc.contributor.author	Ortolan A.O.
dc.contributor.author	Caramori G.F.
dc.contributor.author	Frenking G.
dc.contributor.author	Muñoz-Castro A.
dc.date.accessioned	2020-09-02T22:25:09Z
dc.date.available	2020-09-02T22:25:09Z
dc.date.issued	2015
dc.identifier	10.1039/c5nj02384j
dc.identifier.citation	39, 12, 9963-9968
dc.identifier.issn	11440546
dc.identifier.uri	https://hdl.handle.net/20.500.12728/5673
dc.description	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 [(η2:η2:η2-[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. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
dc.language.iso	en
dc.publisher	Royal Society of Chemistry
dc.title	Role of the cation formal charge in cation-π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations
dc.type	Article

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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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