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On the Possible Coordination on a 3MC State Itself? Mechanistic Investigation Using DFT-Based Methods

Laboratoire de Chimie et Physique Quantiques, UMR 5626 CNRS/Université Toulouse 3-Paul Sabatier, Université de Toulouse, 118 route de Narbonne, 31062 Toulouse, France
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Inorganics 2020, 8(2), 15; https://doi.org/10.3390/inorganics8020015
Received: 30 January 2020 / Revised: 14 February 2020 / Accepted: 16 February 2020 / Published: 19 February 2020
(This article belongs to the Special Issue Photochemistry & Photophysics of Transition Metal Complexes)
Understanding light-induced ligand exchange processes is key to the design of efficient light-releasing prodrugs or photochemically driven functional molecules. Previous mechanistic investigations had highlighted the pivotal role of metal-centered (MC) excited states in the initial ligand loss step. The question remains whether they are equally important in the subsequent ligand capture step. This article reports the mechanistic study of direct acetonitrile coordination onto a 3MC state of [Ru(bpy)3]2+, leading to [Ru(bpy)21-bpy)(NCMe)]2+ in a 3MLCT (metal-to-ligand charge transfer) state. Coordination of MeCN is indeed accompanied by the decoordination of one pyridine ring of a bpy ligand. As estimated from Nudged Elastic Band calculations, the energy barrier along the minimum energy path is 20 kcal/mol. Interestingly, the orbital analysis conducted along the reaction path has shown that creation of the metallic vacancy can be achieved by reverting the energetic ordering of key dσ* and bpy-based π* orbitals, resulting in the change of electronic configuration from 3MC to 3MLCT. The approach of the NCMe lone pair contributes to destabilizing the dσ* orbital by electrostatic repulsion. View Full-Text
Keywords: ruthenium polypyridine complex; photochemistry; photosolvolysis mechanism; metal-centered excited states; triplet state reactivity; nudged elastic band; DFT; molecular orbitals ruthenium polypyridine complex; photochemistry; photosolvolysis mechanism; metal-centered excited states; triplet state reactivity; nudged elastic band; DFT; molecular orbitals
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Soupart, A.; Alary, F.; Heully, J.-L.; Dixon, I.M. On the Possible Coordination on a 3MC State Itself? Mechanistic Investigation Using DFT-Based Methods. Inorganics 2020, 8, 15.

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