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

Cheng, Jun; Chen, Qi; Leng, Xuebing1; Ouyang, Zhongwen; Wang, Zhenxing; Ye, Shengfa; Deng, Liang

doi:10.1016/j.chempr.2018.09.002

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

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Ye, Shengfa
Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

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.

Cite as: https://hdl.handle.net/21.11116/0000-0002-B99D-D

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(η²:η²-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.