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  The Stabilization of Three-Coordinate Formal Mn(0) Complex with NHC and Alkene Ligation

Cheng, J., Chen, Q., Leng, X., Ouyang, Z., Wang, Z., Ye, S., et al. (2018). The Stabilization of Three-Coordinate Formal Mn(0) Complex with NHC and Alkene Ligation. Chem, 4(12), 2844-2860. doi:10.1016/j.chempr.2018.09.002.

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 Creators:
Cheng, Jun1, Author
Chen, Qi1, Author
Leng, Xuebing11, Author
Ouyang, Zhongwen2, Author
Wang, Zhenxing2, Author
Ye, Shengfa3, Author              
Deng, Liang1, Author
Affiliations:
1State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P.R. China, ou_persistent22              
2Wuhan National High Magnetic Field Center & School of Physics, Huazhong University of Science and Technology, Wuhan 430074, P.R. China, ou_persistent22              
3Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              

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Free keywords: low coordinate; manganese; N-heterocyclic carbene; complex; alkene complex
 Abstract: Low-coordinate zero-valent metal species are implicated as key intermediates in various transition-metal-catalyzed and -mediated reactions. However, knowledge on this type of metal species has been mainly restricted to the metals in groups 8–10, and that on the earlier transition-metal analogs is very limited. Herein, we report three-coordinate formal Mn(0) complexes [(NHC)Mn(η22-dvtms)] (NHC = N-heterocyclic carbene, dvtms = divinyltetramethyldisiloxane). Spectroscopic and computational studies established that these formal Mn(0) complexes have an S = 3/2 ground-spin state and feature strong metal-to-alkene π backdonation. As a result of the high covalency of the metal-ligand bonding, these formal Mn(0) complexes are best described as resonance among a series of limiting canonical structures of Mn(0)-dvtms, Mn(II)-[dvtm]2–, and Mn(IV)-[dvtms]4–. These formal Mn(0) complexes can perform reductive coupling with unsaturated hydrocarbons and show diversified reactivity toward H2O, H2, CO, and I2, which hint at the synthetic utility of the three-coordinate formal Mn(0) species.

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Language(s): eng - English
 Dates: 2018-05-282018-09-102018-10-042018-12-13
 Publication Status: Published in print
 Pages: 17
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1016/j.chempr.2018.09.002
 Degree: -

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Title: Chem
Source Genre: Journal
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Publ. Info: Cambridge, MA : Cell Press
Pages: - Volume / Issue: 4 (12) Sequence Number: - Start / End Page: 2844 - 2860 Identifier: ISSN: 2451-9294
CoNE: https://pure.mpg.de/cone/journals/resource/24519294