Highly active and selective supported rhenium catalysts for aerobic oxidation of n-Hexane and n-Heptane

• Autor(a) principal: Mishra, Gopal
• Data de Publicação: 2018
• Outros Autores: Alegria, Elisabete, Pombeiro, Armando, Martins, Luisa
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
• Texto Completo: http://hdl.handle.net/10400.21/8278
• topic: Rhenium; Scorpionate derivative; Immobilization; Supported catalysis; N-alkane; Oxidation; Molecular oxygen; Product selectivity; Radical mechanism

A series of derivative C-scorpionate rhenium complexes, i.e., [ReCl2{NNC(O)C6H5} (Hpz)(PPh3)2] (A) (where Hpz is pyrazole), [ReCl2{NNC(O)C6H5}(Hpz)2(PPh3)] (B), [ReClF {NNC(O)C6H5}(Hpz)2(PPh3)] (C), and their precursor [ReOCl3(PPh3)2] (D), immobilized on 3-aminopropyl-functionalized silica have been prepared and used for neat O2 oxidation of n-hexane and n-heptane mainly to the corresponding alcohols and, in lower amounts, ketones. The supported catalyst C, with fluoro- and diazenido-ligands, exhibits the highest activity for both alkanes (overall turnover numbers (TONs) up to 3.8 _ 103 and 2.5 _ 103, for n-hexane and n-heptane, respectively) and can be reused in consecutive catalytic cycles. Improved conversion was observed after addition of hetero-carboxylate co-catalysts. A free-radical-based mechanism is proposed to explain the product formation.