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一种由双-NHC-CAAC二聚体衍生的双阳离子双自由基。

A bis-NHC-CAAC dimer derived dicationic diradical.

作者信息

Nayak Mithilesh Kumar, Sarkar Pallavi, Elvers Benedict J, Mehta Sakshi, Zhang Fangyuan, Chrysochos Nicolas, Krummenacher Ivo, Vijayakanth Thangavel, Narayanan Ramakirushnan Suriya, Dolai Ramapada, Roy Biswarup, Malik Vishal, Rawat Hemant, Mondal Abhishake, Boomishankar Ramamoorthy, Pati Swapan K, Braunschweig Holger, Schulzke Carola, Ravat Prince, Jana Anukul

机构信息

Tata Institute of Fundamental Research Hyderabad Gopanpally Hyderabad-500107 India

Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research Bangalore-560064 India

出版信息

Chem Sci. 2022 Sep 21;13(42):12533-12539. doi: 10.1039/d2sc03937k. eCollection 2022 Nov 2.

DOI:10.1039/d2sc03937k
PMID:36382295
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9629079/
Abstract

The isolation of carbon-centered diradicals is always challenging due to synthetic difficulties and their limited stability. Herein we report the synthesis of a -1,4-cyclohexylene bridged bis-NHC-CAAC dimer derived thermally stable dicationic diradical. The diradical character of this compound was confirmed by EPR spectroscopy. The variable temperature EPR study suggests the singlet state to be marginally more stable than the triplet state (2 = -5.5 cm (Δ = 0.065 kJ mol)). The presence of the -1,4-cyclohexylene bridge is instrumental for the successful isolation of this dicationic diradical. Notably, in the case of ethylene or propylene bridged bis-NHC-CAAC dimers, the corresponding dicationic diradicals are transient and rearrange to hydrogen abstracted products.

摘要

由于合成困难以及稳定性有限，以碳为中心的双自由基的分离一直具有挑战性。在此，我们报道了一种由 -1,4-亚环己基桥联双-NHC-CAAC二聚体衍生而来的热稳定双阳离子双自由基的合成。该化合物的双自由基特性通过电子顺磁共振光谱得到证实。变温电子顺磁共振研究表明，单重态比三重态略微更稳定（2 = -5.5 cm (Δ = 0.065 kJ mol)）。-1,4-亚环己基桥的存在有助于成功分离这种双阳离子双自由基。值得注意的是，对于乙烯或丙烯桥联的双-NHC-CAAC二聚体，相应的双阳离子双自由基是瞬态的，并重排为氢提取产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/1d96203dc9e1/d2sc03937k-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/08dc00f0e931/d2sc03937k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/0b61668e00f3/d2sc03937k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/0750e4238742/d2sc03937k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/50277e57b17c/d2sc03937k-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/552bb25949a7/d2sc03937k-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/024f476d2608/d2sc03937k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/701e896df40f/d2sc03937k-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/130e0945aaa1/d2sc03937k-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/1d96203dc9e1/d2sc03937k-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/08dc00f0e931/d2sc03937k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/0b61668e00f3/d2sc03937k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/0750e4238742/d2sc03937k-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/50277e57b17c/d2sc03937k-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/552bb25949a7/d2sc03937k-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/024f476d2608/d2sc03937k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/701e896df40f/d2sc03937k-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/130e0945aaa1/d2sc03937k-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f217/9629079/1d96203dc9e1/d2sc03937k-f6.jpg

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