Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer

Bezdek, Máté J.; Chirik, Paul J.

doi:10.1002/ange.201708406

Title: Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer

Journal Article · Wed Jan 31 00:00:00 EST 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201708406· OSTI ID:1418874

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Department of Chemistry Princeton University Frick Laboratory 292 Princeton 08544 USA

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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1418874

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 8; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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