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Updated: Oct 16, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
On the origin of reactivity variation upon sequential ligation: the [Re(Cl)]+/CH4 (x = 1-3) couples
Linghui Yan1,2, Shihan Li1,2, Shaodong Zhou1,2
1College of Chemical and Biological Engineering, Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Zhejiang University, 310027 Hangzhou, P. R. China. szhou@zju.edu.cn.
Abstract:
The potential of [ReCl]+ (x = 1-3) in activating methane has been explored by using a combination of gas-phase experiments and high-level quantum calculations. When the number of Cl ligands increases, the reactivity towards methane activation varies accordingly. While [ReCl]+ (x = 1-2) are able to dehydrogenate methane by a three-state reactivity scenario, [ReCl3]+ shows inertness towards methane at ambient conditions. Furthermore, the product ion [ClRe(H)CH]+ of the [ReCl]+/CH4 couple could continue to activate methane and liberate molecular dihydrogen but another product ion [Cl2ReCH2]+ is unreactive with methane. Obviously, the nature and the number of ligands make a difference to the reactivity towards methane activation. The associated reaction mechanism and the electron origins for the rather different reactivities are discussed in detail. Finally and more importantly, instructive information concerning the rational design of Re-catalysts for methane conversion is obtained.
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