Group 13 metal catalysts for hydrogen activation and hydrogenation

化学 醇盐 催化作用 氢化物 配体(生物化学) 主组元素 反应性(心理学) 金属 氢气储存 过渡金属 无机化学 吡啶 光化学 药物化学 有机化学 受体 替代医学 病理 医学 生物化学
作者
Peiquan Lu,Xiaoyu Zhou,Xiuling Wen,Ruzhao Chen,Cunyuan Zhao,Zhuofeng Ke
出处
期刊:Journal of Catalysis [Elsevier BV]
卷期号:423: 81-93 被引量:2
标识
DOI:10.1016/j.jcat.2023.04.020
摘要

Catalysts with aromatization/dearomatization metal–ligand cooperation paradigm are of increasing interest in the field of hydrogen activation and hydrogenation, with PNP (2,6-bis[(phosphino-methyl]pyridine) as a representative class of ligand. It is highly desired to design PNP catalysts using main group metals to replace transition metals. Herein, a theoretical study of the properties of Group 13 metal (Al, Ga, In) PNP catalysts for hydrogen activation and hydrogenation was performed to comprehensively compare and analyze their catalytic mechanism and reactivity. In sharp contrast to traditional transition metal PNP catalysts that operate an aromatization/dearomatization metal–ligand cooperation, the Group 13 metal PNP catalysts adopt a tetrahedral geometry and prefer a metal-alkoxide promoted cooperation for the hydrogen activation and hydrogenation. The hard and soft acids and bases matching between the metal centers and the alkoxide is found to play a key role in the catalytic properties. PNP-In is found to be the most promising catalyst for hydrogen activation and hydrogenation, which has a proper reaction barrier (26.7 kcal·mol−1) during hydrogen activation because the In center could serve as a relatively softer acceptor for the hydride. The alkoxide bound on the softer Indium center has stronger basicity to deprotonate the PNP ligand or to obtain a proton from the H2 molecule. However, the harder Ga or Al center interacts more strongly with the alkoxide group, hampering the metal-alkoxide promoted protonation during hydrogenation. The bonding analysis and orbital energy analysis indicated that [(PNPtBu)InH(Me)]+ hydride also has a proper activity for the hydrogenation process. In contrast, although [(PNPtBu)AlH(Me)]+ has a much higher activity for hydride transfer, the Al-catalyzed hydrogenation is limited by the benzyloxide bound on the harder Al center, which is less active to assist the H − H bond cleavage or deprotonate the PNPtBu ligand. The Ga catalyst performs in between the best In catalyst and the least active Al catalyst. This understanding of the mechanism and reactivity of Group 13 metal catalysts should be helpful for the development of main group metal catalysts for hydrogen activation and hydrogenation.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
ya发布了新的文献求助10
刚刚
刚刚
练得身形似鹤形完成签到 ,获得积分10
1秒前
1秒前
1秒前
2秒前
鹿港猫妖完成签到,获得积分20
3秒前
chen完成签到,获得积分10
3秒前
4秒前
阿湫发布了新的文献求助10
4秒前
4秒前
5秒前
崔悦欣发布了新的文献求助10
5秒前
希望天下0贩的0应助kk子采纳,获得10
6秒前
丰富的不惜完成签到,获得积分10
8秒前
票子发布了新的文献求助10
8秒前
华仔应助魏莱采纳,获得10
8秒前
F123发布了新的文献求助10
9秒前
shen发布了新的文献求助10
10秒前
10秒前
苗觉觉完成签到,获得积分10
11秒前
帕金森完成签到,获得积分10
12秒前
活力的妙芙完成签到,获得积分10
12秒前
赘婿应助疯子魔煞采纳,获得10
13秒前
橙橙橙完成签到,获得积分10
13秒前
13秒前
你好CDY完成签到,获得积分10
14秒前
14秒前
14秒前
万能图书馆应助希尔伯特采纳,获得10
14秒前
我是老大应助123采纳,获得10
15秒前
芒果小鹌鹑完成签到,获得积分10
16秒前
上官若男应助F123采纳,获得10
17秒前
Singularity应助邢文瑞采纳,获得10
18秒前
c123发布了新的文献求助10
19秒前
嘉嘉琦发布了新的文献求助10
20秒前
wanci应助QWDSA采纳,获得10
22秒前
22秒前
愉快静曼发布了新的文献求助10
25秒前
乐乐乐乐乐乐应助科学家采纳,获得10
26秒前
高分求助中
【提示信息,请勿应助】关于scihub 10000
Les Mantodea de Guyane: Insecta, Polyneoptera [The Mantids of French Guiana] 3000
徐淮辽南地区新元古代叠层石及生物地层 3000
The Mother of All Tableaux: Order, Equivalence, and Geometry in the Large-scale Structure of Optimality Theory 3000
Global Eyelash Assessment scale (GEA) 1000
Picture Books with Same-sex Parented Families: Unintentional Censorship 550
Research on Disturbance Rejection Control Algorithm for Aerial Operation Robots 500
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 4038446
求助须知:如何正确求助?哪些是违规求助? 3576149
关于积分的说明 11374627
捐赠科研通 3305875
什么是DOI,文献DOI怎么找? 1819354
邀请新用户注册赠送积分活动 892680
科研通“疑难数据库(出版商)”最低求助积分说明 815048