Catalysis of CO2 reduction by diazapyridinophane complexes of Fe, Co, and Ni: CO2 binding triggered by combined frontier MO associations involving a SOMO

催化作用 限制 结合能 化学 分子轨道 立体化学 药物化学 结晶学 分子 物理 有机化学 机械工程 工程类 核物理学
作者
Yuto Sakaguchi,Arnau Call,Kosei Yamauchi,Ken Sakai
出处
期刊:Dalton Transactions [Royal Society of Chemistry]
卷期号:50 (44): 15983-15995 被引量:7
标识
DOI:10.1039/d1dt01877a
摘要

Our previous study on the photochemical CO2 reduction into CO catalyzed by the diazapyridinophane complexes of Fe, Co, and Ni revealed that (i) the Co catalyst shows the highest TOF but degrades rapidly, (ii) the Fe catalyst exhibits a lower TOF relative to Co but shows higher robustness, giving a higher TON, and (iii) the Ni complex shows no activity (Sakaguchi et al., Chem. Commun., 2019, 55, 8552). Here we show our DFT results unveiling that the Fe and Co catalysts can utilize multiple sets of frontier MO associations at the CO2 binding by including one of the SOMOs in a high-spin d7 Fe(I) and d8 Co(I) center, respectively, giving an increased driving force for these oxidative addition steps. Remarkably, two-electron reduction of CO2 to CO22- at the binding step is driven by the two electrons transferred from different d-based orbitals. The CoI species binds CO2 at the rate-limiting step with an activation barrier of 15.0 kcal mol-1, rationalizing the high initial TOF observed. However, the CoI(CO) species is given as a dead-end product, consistent with its relatively rapid deactivation. The Fe catalyst possesses a slightly higher barrier in CO2 binding (ΔG‡ = 15.8 kcal mol-1) but does not stabilize the FeI(CO) species which readily releases CO (ΔG = 3.5 kcal mol-1). The Ni catalyst has the smallest barrier in CO2 binding (ΔG‡ = 11.5 kcal mol-1) but the CO release is largely prohibited by the dead-end NiI(CO) species, consistent with its inactive character towards CO2 reduction. The combined results all satisfactorily explain the observed catalytic behaviors.
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
在水一方应助lizibelle采纳,获得10
刚刚
hoyden完成签到,获得积分10
刚刚
Stardust发布了新的文献求助10
1秒前
3秒前
momo发布了新的文献求助10
4秒前
4秒前
乐乐应助Mo采纳,获得10
5秒前
5秒前
Liufgui应助Z6kjoA采纳,获得20
5秒前
爆米花应助科研通管家采纳,获得10
7秒前
NexusExplorer应助科研通管家采纳,获得10
7秒前
cangy发布了新的文献求助10
7秒前
英姑应助科研通管家采纳,获得10
7秒前
地表飞猪应助科研通管家采纳,获得10
7秒前
桐桐应助科研通管家采纳,获得10
7秒前
8秒前
Akim应助科研通管家采纳,获得10
8秒前
Orange应助科研通管家采纳,获得10
8秒前
地表飞猪应助科研通管家采纳,获得10
8秒前
科研通AI2S应助科研通管家采纳,获得10
8秒前
酷波er应助科研通管家采纳,获得10
8秒前
地表飞猪应助科研通管家采纳,获得10
8秒前
8秒前
YamDaamCaa应助科研通管家采纳,获得30
8秒前
luo关闭了luo文献求助
9秒前
Jogging完成签到,获得积分10
10秒前
Villanellel发布了新的文献求助30
10秒前
李健应助ttt采纳,获得10
10秒前
科目三应助xueyu采纳,获得10
11秒前
Jello完成签到,获得积分10
14秒前
14秒前
111完成签到,获得积分10
15秒前
qq完成签到 ,获得积分10
15秒前
16秒前
hhhblabla应助ZZZ采纳,获得20
16秒前
16秒前
打打应助雨的痕迹采纳,获得10
18秒前
18秒前
好好发布了新的文献求助10
19秒前
西海岸的风完成签到 ,获得积分10
19秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
‘Unruly’ Children: Historical Fieldnotes and Learning Morality in a Taiwan Village (New Departures in Anthropology) 400
Indomethacinのヒトにおける経皮吸収 400
Phylogenetic study of the order Polydesmida (Myriapoda: Diplopoda) 370
基于可调谐半导体激光吸收光谱技术泄漏气体检测系统的研究 350
Robot-supported joining of reinforcement textiles with one-sided sewing heads 320
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 3989334
求助须知:如何正确求助?哪些是违规求助? 3531428
关于积分的说明 11253936
捐赠科研通 3270119
什么是DOI,文献DOI怎么找? 1804887
邀请新用户注册赠送积分活动 882087
科研通“疑难数据库(出版商)”最低求助积分说明 809173