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Mechanistic insight into Ni-mediated decarbonylation of unstrained ketones: the origin of decarbonylation catalytic activity†
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2018-06-21 00:00:00 , DOI: 10.1039/c8qo00335a Langhuan Jiang 1, 2, 3, 4, 5 , Fang Huang 1, 2, 3, 4, 5 , Qiong Wang 1, 2, 3, 4, 5 , Chuanzhi Sun 1, 2, 3, 4, 5 , Jianbiao Liu 1, 2, 3, 4, 5 , Dezhan Chen 1, 2, 3, 4, 5
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2018-06-21 00:00:00 , DOI: 10.1039/c8qo00335a Langhuan Jiang 1, 2, 3, 4, 5 , Fang Huang 1, 2, 3, 4, 5 , Qiong Wang 1, 2, 3, 4, 5 , Chuanzhi Sun 1, 2, 3, 4, 5 , Jianbiao Liu 1, 2, 3, 4, 5 , Dezhan Chen 1, 2, 3, 4, 5
Affiliation
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Mechanistic details of the decarbonylation of unstrained ketones by (IMesMe)Ni and (IMesMe)NiCO complexes with a N-heterocyclic carbene ligand (IMesMe) have been explored by density functional theory calculations. The calculated mechanism sheds light on the origin of realization for the decarbonylation catalytic cycle. (IMesMe)Ni mediates the first decarbonylation cycle and generates a biaryl product and (IMesMe)NiCO, which is inactive for the substrate 4-methyl-4′-trifluoromethyl benzophenone 1. However, (IMesMe)NiCO can mediate the decarbonylation of 3-quinolinyl ketone 2 and realize the catalytic cycle. The decarbonylation step is the rate-determining step controlling whether the transformation can be mediated catalytically. The stabilization energy E(2) of BDC(![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O)–C(methyl phenyl) → LVNi for the decarbonylation transition state plays a dominant role in the catalytic cycle. In addition, an electron-withdrawing group on the arene can stabilize the orbital energies facilitating the initial C–C(O) oxidative addition step. A moderate linear correlation is observed between the oxidative addition barriers and the charges transferred from (IMesMe)Ni to the benzoyl moiety.
中文翻译：
Ni介导的未应变酮的脱羰机理的机械洞察力：脱羰催化活性的起源†
通过密度泛函理论计算探索了（IMes Me）Ni和具有N杂环卡宾配体（IMes Me）的（IMes Me）Ni和（IMes Me）NiCO配合物对未应变酮进行脱羰的机理的细节。所计算的机理为脱羰催化循环的实现起点提供了启示。（IMes Me）Ni介导第一个脱羰循环并生成联芳基产物和（IMes Me）NiCO，后者对底物4-甲基-4'-三氟甲基二苯甲酮1无效。然而，（IMes Me）NiCO可以介导3-喹啉基酮2的脱羰作用并实现催化循环。脱羰步骤是控制转化是否可以催化介导的速率确定步骤。BD C（O）–C（甲基苯基） →LV Ni的脱羰过渡态的稳定能E （2）在催化循环中起主要作用。此外，芳烃上的吸电子基团可以稳定轨道能量，从而促进初始的C–C（O）氧化加成步骤。在氧化加成壁垒和从（IMes Me）Ni转移到苯甲酰基部分的电荷之间观察到适度的线性相关性。
更新日期：2018-06-21
O)–C(methyl phenyl) → LVNi for the decarbonylation transition state plays a dominant role in the catalytic cycle. In addition, an electron-withdrawing group on the arene can stabilize the orbital energies facilitating the initial C–C(O) oxidative addition step. A moderate linear correlation is observed between the oxidative addition barriers and the charges transferred from (IMesMe)Ni to the benzoyl moiety.
中文翻译：
Ni介导的未应变酮的脱羰机理的机械洞察力：脱羰催化活性的起源†
通过密度泛函理论计算探索了（IMes Me）Ni和具有N杂环卡宾配体（IMes Me）的（IMes Me）Ni和（IMes Me）NiCO配合物对未应变酮进行脱羰的机理的细节。所计算的机理为脱羰催化循环的实现起点提供了启示。（IMes Me）Ni介导第一个脱羰循环并生成联芳基产物和（IMes Me）NiCO，后者对底物4-甲基-4'-三氟甲基二苯甲酮1无效。然而，（IMes Me）NiCO可以介导3-喹啉基酮2的脱羰作用并实现催化循环。脱羰步骤是控制转化是否可以催化介导的速率确定步骤。BD C（O）–C（甲基苯基） →LV Ni的脱羰过渡态的稳定能E （2）在催化循环中起主要作用。此外，芳烃上的吸电子基团可以稳定轨道能量，从而促进初始的C–C（O）氧化加成步骤。在氧化加成壁垒和从（IMes Me）Ni转移到苯甲酰基部分的电荷之间观察到适度的线性相关性。
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