Interconversion of Molybdenum Imido and Amido Complexes by Proton-Coupled Electron Transfer
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Date
2018-02-19Type
- Journal Article
ETH Bibliography
no
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Abstract
Interconversion of the molybdenum amido [(PhTpy)(PPh2Me)2Mo(NHtBuAr)][BArF24] (PhTpy=4′-Ph-2,2′,6′,2“-terpyridine; tBuAr=4-tert-butyl-C6H4; ArF24=(C6H3-3,5-(CF3)2)4) and imido [(PhTpy)(PPh2Me)2Mo(NtBuAr)][BArF24] complexes has been accomplished by proton-coupled electron transfer. The 2,4,6-tri-tert-butylphenoxyl radical was used as an oxidant and the non-classical ammine complex [(PhTpy)(PPh2Me)2Mo(NH3)][BArF24] as the reductant. The N−H bond dissociation free energy (BDFE) of the amido N−H bond formed and cleaved in the sequence was experimentally bracketed between 45.8 and 52.3 kcal mol−1, in agreement with a DFT-computed value of 48 kcal mol−1. The N−H BDFE in combination with electrochemical data eliminate proton transfer as the first step in the N−H bond-forming sequence and favor initial electron transfer or concerted pathways. Show more
Publication status
publishedExternal links
Journal / series
Angewandte Chemie. International EditionVolume
Pages / Article No.
Publisher
Wiley-VCHOrganisational unit
09759 - Bezdek, Máté József / Bezdek, Máté József
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ETH Bibliography
no
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