posted on 2023-01-03, 15:08authored byHaoyi Li, Muchun Fei, Jennifer L. Troiano, Lu Ma, Xingxu Yan, Peter Tieu, Yucheng Yuan, Yuhan Zhang, Tianying Liu, Xiaoqing Pan, Gary W. Brudvig, Dunwei Wang
Oxidative
methane (CH4) carbonylation promises a direct
route to the synthesis of value-added oxygenates such as acetic acid
(CH3COOH). Here, we report a strategy to realize oxidative
CH4 carbonylation through immobilized Ir complexes on an
oxide support. Our immobilization approach not only enables direct
CH4 activation but also allows for easy separation and
reutilization of the catalyst. Furthermore, we show that a key step,
methyl migration, that forms a C–C bond, is sensitive to the
electrophilicity of carbonyl, which can be tuned by a gentle reduction
to the Ir centers. While the as-prepared catalyst that mainly featured
Ir(IV) preferred CH3COOH production, a reduced catalyst
featuring predominantly Ir(III) led to a significant increase of CH3OH production at the expense of the reduced yield of CH3COOH.