Synthesis and Reactivity of a Cobalt-Supported Singlet Nitrene

化学 硝基苯 光化学 单重态 电子顺磁共振 反应性(心理学) 结晶学 有机化学 激发态 核磁共振 物理 病理 催化作用 核物理学 医学 替代医学
作者
Weiqing Mao,Zihan Zhang,Dominik Fehn,Sergio A. V. Jannuzzi,Frank W. Heinemann,Andreas Scheurer,Maurice van Gastel,Serena DeBeer,Dominik Munz,Karsten Meyer
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:145 (25): 13650-13662 被引量:23
标识
DOI:10.1021/jacs.3c01478
摘要

The synthesis, characterization, and reactivity of a series of cobalt terminal imido complexes supported by an N-anchored tripodal tris(carbene) chelate is described, including a Co-supported singlet nitrene. Reaction of the CoI precursor [(TIMMNmes)CoI](PF6) (TIMMNmes = tris-[2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with p-methoxyphenyl azide yields a CoIII imide [(TIMMNmes)CoIII(NAnisole)](PF6) (1). Treatment of 1 with 1 equiv of [FeCp2](PF6) at -35 °C affords a formal CoIV imido complex [(TIMMNmes)Co(NAnisole)](PF6)2 (2), which features a bent Co-N(imido)-C(Anisole) linkage. Subsequent one-electron oxidation of 2 with 1 equiv of AgPF6 provides access to the tricationic cobalt imido complex [(TIMMNmes)Co(NAnisole)](PF6)3 (3). All complexes were fully characterized, including single-crystal X-ray diffraction (SC-XRD) analyses, infrared (IR) vibrational, ultraviolet/visible (UV/vis) electronic absorption, multinuclear NMR, X-band electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and high-energy-resolution fluorescence-detected X-ray absorption spectroscopy (HERFD XAS). Quantum chemical calculations provide additional insight into the electronic structures of all compounds. The dicationic CoIV imido complex 2 exhibits a doublet ground state with considerable imidyl character as a result of covalent Co-NAnisole bonding. At room temperature, 2 readily converts to a CoII amine complex involving intramolecular C-H bond amination. Electronically, tricationic complex 3 can be understood as a singlet nitrene bound to CoIII with significant CoIV imidyl radical character. Verifying the pronounced electrophilicity, nucleophiles such as H2O and tBuNH2 add to 3─analogous to the parent free nitrene─in the para position of the aromatic substituent, thus, clearly corroborating singlet nitrene-type reactivity.
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
Teko发布了新的文献求助10
1秒前
Akim应助油个大饼呜呜呜采纳,获得10
1秒前
chris完成签到,获得积分10
1秒前
FXQ123_范发布了新的文献求助10
1秒前
1秒前
2秒前
2秒前
4秒前
4秒前
机灵飞阳发布了新的文献求助10
6秒前
7秒前
7秒前
8秒前
8秒前
斯文败类应助Teko采纳,获得10
8秒前
脑洞疼应助小左采纳,获得10
10秒前
12秒前
嗯嗯发布了新的文献求助10
13秒前
13秒前
浮生发布了新的文献求助10
13秒前
14秒前
Teko完成签到,获得积分10
17秒前
英俊的铭应助程之杭采纳,获得10
17秒前
20秒前
喻义梅发布了新的文献求助10
20秒前
jk发布了新的文献求助10
21秒前
可爱的安萱完成签到,获得积分10
23秒前
orixero应助尼莫采纳,获得10
24秒前
25秒前
泡面完成签到 ,获得积分10
25秒前
25秒前
26秒前
26秒前
JUdy发布了新的文献求助20
27秒前
SYLH应助蓝天白云采纳,获得30
28秒前
受伤邴完成签到 ,获得积分10
29秒前
ZZZ发布了新的文献求助10
29秒前
华仔发布了新的文献求助20
30秒前
30秒前
DijiaXu应助猪猪hero采纳,获得10
35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 3989263
求助须知:如何正确求助?哪些是违规求助? 3531418
关于积分的说明 11253814
捐赠科研通 3270066
什么是DOI,文献DOI怎么找? 1804884
邀请新用户注册赠送积分活动 882084
科研通“疑难数据库(出版商)”最低求助积分说明 809136