烷烃的均相氧化:铑-烷基配合物的作用

IF 5.062

Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI:10.1016/j.molcata.2016.07.026

E.G. Chepaikin , A.P. Bezruchenko , G.N. Menchikova , А.Е. Gekhman

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引用次数: 15

摘要

在全氟羧酸(CF3COOH, C3F7COOH)水溶液中，RhCl3-KI-NaCl和RhCl3-Cu (OAcf) 2-NaCl催化体系对烷烃和一氧化碳的双氧耦合氧化是有效的。在它们存在的情况下，主要是在过氧铑作为氧化剂的参与下，外球将烷烃氧化成相应的酯(醇)(机制A)。该过程部分地通过涉及rh -烷基中间体的内球机制B发生。机理B由(a)烷基氯化物的形成，(B)甲烷转化过程中醋酸的合成，以及(c)丙烷氧化过程中的位置选择性支持。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Homogeneous oxidation of alkanes: Role of rhodium–alkyl complexes

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Homogeneous oxidation of alkanes: Role of rhodium–alkyl complexes

Catalytic systems RhCl₃–KI–NaCl and RhCl₃–Cu(OAc_f)₂–NaCl in aqueous perfluorinated carboxylic acids (CF₃COOH, C₃F₇COOH) are effective in coupled oxidation of alkanes and carbon monoxide with dioxygen. In their presence, predominant is the outer-sphere oxidation of alkanes into respective esters (alcohols) with involvement of peroxo rhodium species as an oxidant (mechanism A). The process occurs partially by the inner-sphere mechanism B involving Rh–alkyl intermediates. Mechanism B is supported by (a) formation of alkyl chlorides, (b) synthesis of acetic acid in conversion of methane, and (c) positional selectivity in oxidation of propane.

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来源期刊

Journal of Molecular Catalysis A: Chemical 化学-物理化学

自引率

0.00%

发文量

审稿时长

2.8 months

期刊介绍： The Journal of Molecular Catalysis A: Chemical publishes original, rigorous, and scholarly full papers that examine the molecular and atomic aspects of catalytic activation and reaction mechanisms in homogeneous catalysis, heterogeneous catalysis (including supported organometallic catalysis), and computational catalysis.