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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computational Insight into the Mechanism of Ruthenium(II)Catalyzed alpha-Alkylation of Arylmethyl Nitriles Using Alcohols
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Computational Insight into the Mechanism of Ruthenium(II)Catalyzed alpha-Alkylation of Arylmethyl Nitriles Using Alcohols

机译：使用醇使用醇催化钌（II）钌（II）催化α-烷基化的α-烷基化的洞察力

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摘要

The ruthenium(II)-catalyzed alpha-alkylation reaction of arylmethyl nitriles (phenylacetonitrile) using alcohols (ethanol) in toluene has been extensively investigated by means of SMD-M06-2X/6-311G(d,p)-LANL2dz (LAnL2dz for Ru, 6-311G(d,p) for other atoms) calculations. Detailed mechanistic schemes have been proposed and discussed. The catalytically active Ru(II) complex was generated by the base-induced KCl elimination from the catalyst precursor [(PNPPh)-RuHCl(CO)]. The overall Ru(II) catalytic cycle consists of three basic processes: (1) ethanol-to-aldehyde transformation catalyzed by the 16-electron unsaturated ruthenium pincer catalyst; (2) a 16-electron unsaturated ruthenium pincer catalyst catalyzed condensation reaction of arylmethyl nitrile with aldehyde, which leads to PhC(CN)=CHCH3 ; (3) hydrogenation of PhC(CN)=CHCH3, which leads to the formation of the alpha-alkylated arylmethyl nitrile product (PhCH(CH2CH3)CN). The DFT results revealed that the rate-determining barrier of the overall reaction was 23.9 kcal/mol of the H-transfer step in the third process. The reaction of PhC(CN)=CHCH3 with the dihydride Ru complex, which is generated in the ethanol-to-aldehyde transformation process, is the more preferable hydrogenation mechanism than hydrogenation of vinyl nitrile-Ru complex by H-2. Using alcohol as the reactant not only fulfills the requirement of the borrowing-H strategy but also lowers the barriers of the H-migration steps.
机译：使用在甲苯醇（乙醇）的钌（II）芳甲基腈的催化的的α-烷基化反应（苯基乙腈）已经SMD-M06-2X / 6-311G（d，p）的-LANL2dz的手段被广泛地研究（LANL2DZ用于RU，6-311G（d，p）的其他原子）的计算。详细机制方案被提出和讨论。通过从催化剂前体[（PNPPh）-RuHCl（CO）]的碱诱导的KCl消除所产生的催化活性的Ru（II）络合物。整体的Ru（II）催化循环包括三个基本过程：由16电子不饱和钌钳形催化剂催化（1）乙醇到醛转化; （2）16电子不饱和钌钳形用醛，芳甲基腈的催化剂催化缩合反应，这导致光子晶体（CN）= CHCH 3; （3）光子晶体（CN）= CHCH 3的氢化，这导致所述α-烷基化的芳甲基腈产物（物理信道（CH 2 CH 3）CN）的形成。在DFT结果表明，总的反应的速率决定屏障是在第三过程中的H-转印步骤23.9千卡/摩尔。光子晶体（CN）= CHCH 3与二氢化钌络合物，其在乙醇到醛转化过程中产生的反应，比乙烯基腈茹由H-2复合物的氢化更优选的氢化的机制。使用酒精作为反应物不仅满足借款-H策略的要求也降低的H-迁移步骤的障碍。

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