A DFT-based mechanistic proposal for the light-driven insertion of dioxygen into Pt(II)-C bonds
Fernández-Alvarez, Victor M. (Institut Català d'Investigació Química)
Ho, Sarah K. Y. (Imperial College London. Department of Chemistry)
Britovsek, George J. P. (Imperial College London. Department of Chemistry)
Maseras Cuní, Feliu (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2018
Resum:	The photocatalyzed insertion of dioxygen into the Pt(II)-methyl bond in terpyridine platinum complexes has been shown to proceed efficiently, but its mechanism remains a challenge. In particular, there are serious counter-intuitive differences in the reactivity of structurally similar complexes. M06 calculations in solvent with a valence double-ζ basis set supplemented by polarization and diffusion shells (benchmarked against ωB97x-D calculations with a larger basis set) are able to provide a satisfactory mechanistic answer. The proposed mechanism starts with the absorption of a photon by the metal complex, which then evolves into a triplet state that reacts with the triplet dioxygen fragment. A variety of possible reaction paths have been identified, some leading to the methylperoxo product and others reverting to the reactants, and the validity of some of these paths has been confirmed by additional experiments. The balance between the barriers towards productive and unproductive paths reproduces the diverging experimental behavior of similar complexes and provides a general mechanistic picture for these processes.
Ajuts:	Agencia Estatal de Investigación CTQ2017-87792-R Ministerio de Economía y Competitividad SEV-2013-0319 Ministerio de Economía y Competitividad BES-2012-057655
Nota:	Altres ajuts: CERCA Programme/Generalitat de Catalunya
Nota:	Altres ajuts: The authors also thank COST Action CARISMA CM1205
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	Chemical science, Vol. 9, Issue 22 (June 2018) , p. 5039-5046, ISSN 2041-6539

DOI: 10.1039/C8SC01161C
PMID: 29938033

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