简单的配体改变调控钌配合物催化还原CO2的活性：硼基配体的对位效应和Ru―H键的性质

doi:10.3866/PKU.WHXB201712131

物理化学学报 >> 2018, Vol. 34 >> Issue (10): 1097-1105.doi: 10.3866/PKU.WHXB201712131

所属专题：材料科学的分子模拟

简单的配体改变调控钌配合物催化还原CO₂的活性：硼基配体的对位效应和Ru―H键的性质

刘甜¹,黎军^1,*(),刘维佳²,朱育丹^1,*(),陆小华¹

¹ 南京工业大学化工学院、材料化学工程国家重点实验室，南京 210009
² 南京市锅炉压力容器检验研究院，南京 210019

收稿日期:2017-11-15 发布日期:2018-04-13
通讯作者: 黎军,朱育丹 E-mail:lijun@njtech.edu.cn;ydzhu@njtech.edu.cn
基金资助:
国家重点基础研究发展计划(973)(2013CB733505);国家重点基础研究发展计划(973)(2013CB733501);国家自然科学基金(91334202);江苏省自然科学基金(BK2012421);国家教育部高等学校博士点基金(20123221120015);江苏省高校优势学科建设工程资助项目

Simple Ligand Modifications to Modulate the Activity of Ruthenium Catalysts for CO₂ Hydrogenation: Trans Influence of Boryl Ligands and Nature of Ru―H Bond

Tian LIU¹,Jun LI^1,*(),Weijia LIU²,Yudan ZHU^1,*(),Xiaohua LU¹

¹ College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu Province, P. R. China
² Nanjing Boiler and Pressure Vessel Inspection Institute, Nanjing 210019, Jiangsu Province, P. R. China

Received:2017-11-15 Published:2018-04-13
Contact: Jun LI,Yudan ZHU E-mail:lijun@njtech.edu.cn;ydzhu@njtech.edu.cn
Supported by:
National Key Basic Research Development Program of China (973)(2013CB733505);National Key Basic Research Development Program of China (973)(2013CB733501);National Natural Science Foundation of China(91334202);Natural Science Foundation of Jiangsu Province(BK2012421);Research Fund for the Doctoral Program of Higher Education of China(20123221120015);Project for Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)

摘要/Abstract

摘要：

开发高效的催化剂用于催化还原CO₂转化为甲酸和它的盐类已经成为研究的热点，是因为将CO₂转化为C1产物不仅可以解决CO₂的含量升高带来的环境问题，还可以解决化石能源燃烧日趋严重的问题。贵金属配合物催化CO₂转化为甲酸和甲酸盐类是目前这类反应最有效的方式，尤其是Ru、Ir和Rh等贵金属。我们之前的研究结果表明Ir(Ⅲ), Ru(Ⅱ)类配合物催化还原CO₂转化为甲酸盐的活性是由配合物Ru―H键的成键性质决定的。它们能高活性的催化CO₂是由于它们都含有同一种特点的Ru―H键，是由Ru的sd²杂化轨道和H的1s轨道杂化而成的，而且这一特点可以被活性氢的对位配体显著影响。鉴于硼基配体具有强的对位效应，我们基于高活性的均相催化剂Ru(PNP)(CO)H₂ (PNP = 2, 6-二(二叔丁基磷甲基)-吡啶)设计了Ru-PNP-HBcat和Ru-PNP-HBpin，并计算了二者催化还原CO₂的活性。Bcat和Bpin配体是实验上常用的硼基配体。我们的计算结果表明Ru-PNP-HBcat和Ru-PNP-HBpin有比Ru-PNP-H₂更长的Ru―H键、亲核性更强的活性氢，其Ru―H键中的Ru原子的d轨道杂化成分的贡献也比Ru-PNP-H₂的更少。相应地Ru-PNP-HBcat和Ru-PNP-HBpin活化CO₂的能垒比Ru-PNP-H₂低。而且Ru-PNP-H₂、Ru-PNP-HBcat和Ru-PNP-HBpin催化CO₂转化为甲酸盐的能垒分别为76.2、67.8、54.4 kJ∙mol^-1，表明Ru-PNP-HBpin具有最高的催化活性。因此，钌配合物催化还原CO₂的活性可由硼基配体强的对位效应和Ru―H键的成键性质来调控。

关键词: CO₂还原, 钌配合物, 硼基配体, 对位效应, Ru―H键

Abstract:

The development of efficient catalysts for the hydrogenation of CO₂ to formic acid (FA) or formate has attracted significant interest as it can address the increasingly severe energy crisis and environmental problems. One of the most efficient methods to transform CO₂ to FA is catalytic homogeneous hydrogenation using noble metal catalysts based on Ir, Ru, and Rh. In our previous work, we demonstrated that the activity of CO₂ hydrogenation via direct addition of hydride to CO₂ on Ir(Ⅲ) and Ru(Ⅱ) complexes was determined by the nature of the metal-hydride bond. These complexes could react with the highly stable CO₂ molecule because they contain the same distinct metal-hydride bond formed from the mixing of the sd² hybrid orbital of metal with the 1s orbital of H, and evidently, this property can be influenced by the trans ligand. Since boryl ligands exhibit a strong trans influence, we proposed that introducing such ligands may enhance the activity of the Ru―H bond by weakening it as a result of the trans influence. In this work, we designed two potential catalysts, namely, Ru-PNP-HBcat and Ru-PNP-HBpin, which were based on the Ru(PNP)(CO)H₂ (PNP = 2, 6-bis(dialkylphosphinomethyl)pyridine) complex, and computationally investigated their reactivity toward CO₂ hydrogenation. Bcat and Bpin (cat = catecholate, pin = pinacolate) are among the most popular boryl ligands in transition metal boryl complexes and have been widely applied in catalytic reactions. Our optimization results revealed that the complexes modified by boryl ligands possessed a longer Ru―H bond. Similarly, natural bond orbital (NBO) charge analysis indicated that the nucleophilic character of the hydride in Ru-PNP-HBcat and Ru-PNP-HBpin was higher as compared to that in Ru-PNP-H₂. NBO analysis of the nature of Ru―H bond indicated that these complexes also followed the law of the bonding of Ru―H bond proved in the previous works (Bull. Chem. Soc. Jpn. 2011, 84 (10), 1039; Bull. Chem. Soc. Jpn. 2016, 89 (8), 905), and the d orbital contribution of the Ru atom in Ru-PNP-HBcat and Ru-PNP-HBpin was smaller than that in Ru-PNP-H₂. Consequently, the Ru-PNP-HBcat and Ru-PNP-HBpin complexes were more active than Ru-PNP-H₂ for the direct hydride addition to CO₂ because of the lower activation energy barrier, i.e., from 29.3 kJ∙mol^-1 down to 24.7 and 23.4 kJ∙mol^-1, respectively. In order to further verify our proposed catalyst-design strategy for CO₂ hydrogenation, the free energy barriers of the complete pathway for the hydrogenation of CO₂ to formate catalyzed by complexes Ru-PNP-H₂, Ru-PNP-HBcat, and Ru-PNP-HBpin were calculated to be 76.2, 67.8, and 54.4 kJ∙mol^-1, respectively, indicating the highest activity of Ru-PNP-HBpin. Thus, the reactivity of Ru catalysts for CO₂ hydrogenation could be tailored by the strong trans influence of the boryl ligands and the nature of the Ru―H bond.

Key words: CO₂ hydrogenation, Ru complex, Boryl ligand, Trans influence, Ru―H bond

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刘甜,黎军,刘维佳,朱育丹,陆小华. 简单的配体改变调控钌配合物催化还原CO₂的活性：硼基配体的对位效应和Ru―H键的性质[J]. 物理化学学报, 2018, 34(10), 1097-1105. doi: 10.3866/PKU.WHXB201712131

Tian LIU,Jun LI,Weijia LIU,Yudan ZHU,Xiaohua LU. Simple Ligand Modifications to Modulate the Activity of Ruthenium Catalysts for CO₂ Hydrogenation: Trans Influence of Boryl Ligands and Nature of Ru―H Bond[J]. Acta Phys. -Chim. Sin. 2018, 34(10), 1097-1105. doi: 10.3866/PKU.WHXB201712131

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201712131

https://www.whxb.pku.edu.cn/CN/Y2018/V34/I10/1097

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简单的配体改变调控钌配合物催化还原CO₂的活性：硼基配体的对位效应和Ru―H键的性质

Simple Ligand Modifications to Modulate the Activity of Ruthenium Catalysts for CO₂ Hydrogenation: Trans Influence of Boryl Ligands and Nature of Ru―H Bond

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