Theoretical Mechanism of Rh-Containing Species Catalyzing the Hydrogenolysis of Lignin Model Compounds Using -CαO-H and -Cα-H Groups as Superior H-Sources.

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
The Journal of Physical Chemistry B Pub Date : 2024-12-19 Epub Date: 2024-12-04 DOI:10.1021/acs.jpcb.4c06298
Han-Yun Min, Jin-Shan Xiong, Ting-Hao Liu, Jin-Tao Gou, Chang-Wei Hu, Hua-Qing Yang
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引用次数: 0

Abstract

The hydrogenolysis of lignin model compounds (MCs) into high-value chemicals has received increasing attention, but their catalytic reaction mechanisms are not yet very clear. Here, we report the reaction mechanisms of the hydrogenolysis of MC into 4-acetylanisole (AAL) and guaiacol (GAL) catalyzed by LRuCl3 (L = 4'-(4-methoxyphenyl)-2,2':6',2″-terpyridine) with MC, H2, and 1-phenylethan-1-ol (PEO) as the H-sources in aqueous solution with the Bro̷nsted base (NaOH), at the M06/def2-TZVP, 6-311++G (d,p) theoretical level, namely, RS-Self, RS-H2, and RS-PEO, respectively. After dissociation in NaOH aqueous solution, the LRuCl3 compound can form a stable complex LRh (OH)3 as the initial catalytically active species. Their rate-determining steps are related to the cleavage of the -CαO-H bond in both RS-Self-and RS-PEO, whereas it is associated with the heterolysis of the H-H bond in RS-H2. From NaOH aqueous solution, the OH- ligand of LRh(OH)3 promotes the cleavage of the -CαO-H bond with MC and PEO as H-sources, whereas it advances the heterolysis of the H-H bond with H2 as the H-source, owing to its strong Bro̷nsted basicity. Furthermore, the Rh center of LRh(OH)3 mediates the cleavage of the -Cα-H bond, because of its Lewis acidity. The reaction activity lowers as RS-Self > RS-PEO ≫ RS-H2, which is positively dependent on the protonation degree of the departing H atom. Compounds containing both -CαO-H and -Cα-H groups can act as effective donors for H-sources. In the meantime, the stronger the electron-withdrawing groups they contain, the more pronounced the protonation of the -CαO-H group and the higher the reaction activity in providing H-sources. The present results provide insights into utilizing lignin's own functional groups as a hydrogen source for high-value conversion.

含rh物质以-CαO-H和-Cα-H基团为优h源催化木质素模型化合物氢解的理论机理
木质素模型化合物(MCs)的氢解制备高价值化学品受到越来越多的关注,但其催化反应机理尚不十分清楚。本文报道了LRuCl3 (L = 4′-(4-甲氧基苯基)-2,2′:6′,2″-三吡啶)催化MC、H2和1-苯基比-1醇(PEO)为h源,在水溶液中与Bro′est碱(NaOH)在M06/def2-TZVP, 6-311++G (d,p)理论水平下,即RS-Self、RS-H2和RS-PEO催化下,MC氢解成4-乙酰氨基苯醚(AAL)和愈创木酚(GAL)的反应机理。LRuCl3化合物在NaOH水溶液中解离后,可形成稳定的配合物LRh (OH)3作为初始催化活性物质。它们的速率决定步骤与rs - self和RS-PEO中-CαO-H键的裂解有关,而与RS-H2中H-H键的异裂有关。在NaOH水溶液中,LRh(OH)3的OH-配体以MC和PEO为h源促进- c - α - o - h键的断裂,而以H2为h源促进H-H键的异裂,这是由于LRh(OH)3具有较强的Bro - st碱性。此外,LRh(OH)3的Rh中心由于其Lewis酸性介导了- c - α- h键的断裂。反应活度随RS-Self > RS-PEO比RS-H2低而降低,其活度与H原子的质子化程度呈正相关。含有-CαO-H和-Cα-H基团的化合物可以作为h源的有效供体。同时,吸电子基团越强,- c - α - o - h基团质子化越明显,提供h源的反应活性越高。目前的结果为利用木质素本身的官能团作为高价值转化的氢源提供了见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
5.80
自引率
9.10%
发文量
965
审稿时长
1.6 months
期刊介绍: An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.
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