化学
催化作用
乙炔
氧化还原
催化循环
还原消去
镍
异构化
光化学
部分
金属环
反应机理
药物化学
立体化学
无机化学
有机化学
X射线晶体学
物理
衍射
光学
摘要
The (nitro)( N ‐methyldithiocarbamato)(trimethylphospane)nickel(II), [Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex catalyses efficiently the O‐atom transfer reactions to CO and acetylene. Energetically feasible sequence of elementary steps involved in the catalytic cycle of the air oxidation of CO and acetylene are proposed promoted by the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] ↔ Ni(NO 2 )(S 2 CNHMe)(PMe 3 ) redox couple using DFT methods both in vacuum and dichloromethane solutions. The catalytic air oxidation of HC≡CH involves formation of a five‐member metallacycle intermediate, via a [3 + 2] cyclo‐addition reaction of HC≡CH to the Ni‐N = O moiety of the Ni(NO 2 )(S 2 CNHMe)(PMe 3 )] complex, followed by a β H‐atom migration toward the C α carbon atom of the coordinated acetylene and release of the oxidation product (ketene). The geometric and energetic reaction profile for the reversible [Ni( ‐NO 2 )(S 2 CNHMe)(PMe 3 )] [Ni( ‐ONO)(S 2 CNHMe)(PMe 3 )] linkage isomerization has also been modeled by DFT calculations. © 2017 Wiley Periodicals, Inc.
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