Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer
Abstract
Abstract Interconversion of the molybdenum amido [( Ph Tpy)(PPh 2 Me) 2 Mo(NH t BuAr)][BArF 24 ] ( Ph Tpy=4′‐Ph‐2,2′,6′,2“‐terpyridine; t BuAr=4‐ tert ‐butyl‐C 6 H 4 ; ArF 24 =(C 6 H 3 ‐3,5‐(CF 3 ) 2 ) 4 ) and imido [( Ph Tpy)(PPh 2 Me) 2 Mo(N t BuAr)][BArF 24 ] 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 [( Ph Tpy)(PPh 2 Me) 2 Mo(NH 3 )][BArF 24 ] 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.
- Authors:
-
[1];
[1]
- Department of Chemistry Princeton University Frick Laboratory 292 Princeton 08544 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1418874
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 8; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Bezdek, Máté J., and Chirik, Paul J. Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer. Germany: N. p., 2018.
Web. doi:10.1002/ange.201708406.
Bezdek, Máté J., & Chirik, Paul J. Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer. Germany. https://doi.org/10.1002/ange.201708406
Bezdek, Máté J., and Chirik, Paul J. Wed .
"Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer". Germany. https://doi.org/10.1002/ange.201708406.
@article{osti_1418874,
title = {Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer},
author = {Bezdek, Máté J. and Chirik, Paul J.},
abstractNote = {Abstract Interconversion of the molybdenum amido [( Ph Tpy)(PPh 2 Me) 2 Mo(NH t BuAr)][BArF 24 ] ( Ph Tpy=4′‐Ph‐2,2′,6′,2“‐terpyridine; t BuAr=4‐ tert ‐butyl‐C 6 H 4 ; ArF 24 =(C 6 H 3 ‐3,5‐(CF 3 ) 2 ) 4 ) and imido [( Ph Tpy)(PPh 2 Me) 2 Mo(N t BuAr)][BArF 24 ] 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 [( Ph Tpy)(PPh 2 Me) 2 Mo(NH 3 )][BArF 24 ] 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.},
doi = {10.1002/ange.201708406},
journal = {Angewandte Chemie},
number = 8,
volume = 130,
place = {Germany},
year = {Wed Jan 31 00:00:00 EST 2018},
month = {Wed Jan 31 00:00:00 EST 2018}
}
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