Periodic Trends and Fluxionality Effects on Transition Metal Catalyzed Sulfoxidation.

Autor:	Garay-Ruiz D; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science & Technology (BIST), Av. Països Catalans, 16, 43007 Tarragona, Spain., Zonta C; Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova, Italy.; Consorzio Interuniversitario reattività e Catalisi (CIRCC)-Padova UdR, via Marzolo 1, 35131 Padova, Italy., Lovat S; Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova, Italy., Sanz Azcona F; Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova, Italy.; Consorzio Interuniversitario reattività e Catalisi (CIRCC)-Padova UdR, via Marzolo 1, 35131 Padova, Italy., González-Fabra J; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science & Technology (BIST), Av. Països Catalans, 16, 43007 Tarragona, Spain., Bo C; Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science & Technology (BIST), Av. Països Catalans, 16, 43007 Tarragona, Spain.; Departament de Química Física i Inorgànica, Universitat Rovira i Virgili (URV), C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain., Licini G; Dipartimento di Scienze Chimiche, Università degli Studi di Padova, via Marzolo 1, 35131 Padova, Italy.; Consorzio Interuniversitario reattività e Catalisi (CIRCC)-Padova UdR, via Marzolo 1, 35131 Padova, Italy.
Jazyk:	angličtina
Zdroj:	ACS omega [ACS Omega] 2024 Sep 05; Vol. 9 (37), pp. 38798-38808. Date of Electronic Publication: 2024 Sep 05 (Print Publication: 2024).
DOI:	10.1021/acsomega.4c04831
Abstrakt:	Despite the extended interest in d 0 metal complexes as catalysts for peroxide activation and eventual oxygen transfer processes, there are still gaps in the understanding of how they proceed at the microscopic level. Herein, we have considered sulfide oxidation with cumyl hydroperoxide as a test system, performing the reaction with a series of eight different aminotriphenolate d 0 metal complexes: Ti(IV), Zr(IV), Hf(IV), V(V), Nb(V), Ta(V), Mo(VI), and W(VI). The reactivity and selectivity of the catalytic systems, as well as the effect of a strong Lewis base (dimethylhexyl- N -oxide), have been determined experimentally, correlating kinetic values with Sanderson electronegativity values. Theoretical calculations of the catalytic cycles have been performed to have a clearer description of the role of the reactive peroxo species. Combining experimental results and DFT predictions, we propose suitable mechanisms for all eight metal aminotriphenolates, rationalizing the expected periodic trends, while also unveiling the unique reaction pathways available to highly flexible vanadium complexes. Competing Interests: The authors declare no competing financial interest. (© 2024 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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