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含 -RuCl 基团的 1,4 - 二氮杂丁二烯配体的钌配合物用于醇的催化无受体脱氢反应:化学非惰性配体参与的密度泛函理论证据

Ruthenium complexes of 1,4-diazabutadiene ligands with a -RuCl moiety for catalytic acceptorless dehydrogenation of alcohols: DFT evidence of chemically non-innocent ligand participation.

作者信息

Mukherjee Aparajita, Datta Sayanti, Richmond Michael G, Bhattacharya Samaresh

机构信息

Department of Chemistry, Inorganic Chemistry Section, Jadavpur University Kolkata 700 032 India

Department of Chemistry, Brainware University Kolkata 700 125 India.

出版信息

RSC Adv. 2023 Aug 29;13(36):25660-25672. doi: 10.1039/d3ra04750d. eCollection 2023 Aug 21.

Abstract

The acceptorless dehydrogenative coupling (ADC) of primary alcohols to esters by diazabutadiene-coordinated ruthenium compounds is reported. Treatment of -Ru(dmso)Cl in acetone at 56 °C with different 1,4-diazabutadienes [-XCHN[double bond, length as m-dash]C(H)(H)C[double bond, length as m-dash]NCHX-; X = H, CH, OCH, and Cl; abbreviated as DAB-X], gives -Ru[κ-,-DAB-X]Cl as the kinetic product of substitution. Heating these products in -xylene at 144 °C gives the thermodynamically favored -Ru[κ-,-DAB-X]Cl isomers. Electronic structure calculations confirm the greater stability of the diastereomer. The molecular structures for each pair of geometric isomers have been determined by X-ray diffraction analyses. Cyclic voltammetry experiments on the complexes show an oxidative response and a reductive response within 0.50 to 0.93 V and -0.76 to -1.24 V SCE respectively. The -Ru[κ-,-DAB-X]Cl complexes function as catalyst precursors for the acceptorless dehydrogenative coupling of primary alcohols to H and homo- and cross-coupled esters. When 1,4-butanediol and 1,5-pentanediol are employed as substrates, lactones and hydroxyaldehydes are produced as the major dehydrogenation products, while secondary alcohols afforded ketones in excellent yields. The mechanism for the dehydrogenation of benzyl alcohol to benzyl benzoate and H using -Ru[κ-,-DAB-H]Cl (-1) as a catalyst precursor was investigated by DFT calculations. The data support a catalytic cycle that involves the four-coordinate species Ru[κ-,-DAB-H]κ--DAB-H whose protonated κ-diazabutadiene moiety functions as a chemically non-innocent ligand that facilitates a β-hydrogen elimination from the κ--benzoxide ligand to give the corresponding hydride HRu[κ-,-DAB-H]κ--DAB-H. H production follows a Noyori-type elimination to give (H)Ru[κ-,-DAB-H]κ--DAB-H as an intermediate in the catalytic cycle.

摘要

据报道,重氮丁二烯配位的钌化合物可实现伯醇与酯的无受体脱氢偶联反应(ADC)。在56℃下,于丙酮中用不同的1,4 - 重氮丁二烯[-XCHN═C(H)(H)C═NCHX -;X = H、CH、OCH和Cl;简称为DAB - X]处理-Ru(dmso)Cl,得到取代反应的动力学产物-Ru[κ -,-DAB - X]Cl。在144℃下于-xylene中加热这些产物,可得到热力学上更有利的-Ru[κ -,-DAB - X]Cl异构体。电子结构计算证实了非对映异构体具有更高的稳定性。通过X射线衍射分析确定了每对几何异构体的分子结构。对这些配合物进行的循环伏安法实验表明,在相对于饱和甘汞电极(SCE)分别为0.50至0.93 V和-0.76至-1.24 V的范围内出现氧化响应和还原响应。-Ru[κ -,-DAB - X]Cl配合物可作为催化剂前体,用于伯醇与H以及同偶联和交叉偶联酯的无受体脱氢偶联反应。当使用1,4 - 丁二醇和1,5 - 戊二醇作为底物时,内酯和羟基醛作为主要脱氢产物生成,而仲醇则以优异的产率生成酮。使用-Ru[κ -,-DAB - H]Cl (-1)作为催化剂前体,通过DFT计算研究了苯甲醇脱氢生成苯甲酸苄酯和H的反应机理。数据支持一个催化循环,该循环涉及四配位物种Ru[κ -,-DAB - H][κ - -DAB - H](κ - OCHPh),其质子化的κ - 重氮丁二烯部分作为化学上非惰性的配体,促进从κ - -苯氧基配体进行β - 氢消除,生成相应的氢化物HRu[κ -,-DAB - H][κ - -DAB - H](κ -,-苯甲醛)。H的生成遵循Noyori型消除反应,生成(H)Ru[κ -,-DAB - H][κ - -DAB - H](κ - -苯甲醛)作为催化循环中的中间体。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/cb09/10463240/79edf09d65a3/d3ra04750d-s1.jpg

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