Probing Hydrogen Atom Transfer at a Phosphorus(V) Oxide Bond Using a "bulky Hydrogen Atom" Surrogate: Analogies to PCET

Jiaxiang Chu, Timothy G. Carroll, Guang Wu, Joshua Telser, Roman Dobrovetsky, Gabriel Ménard

Research output: Contribution to journalArticlepeer-review

Abstract

Recent computational studies suggest that the phosphate support in the commercial vanadium phosphate oxide (VPO) catalyst may play a critical role in initiating butane C-H bond activation through a mechanism termed reduction-coupled oxo activation (ROA) similar to proton-coupled electron transfer (PCET); however, no experimental evidence exists to support this mechanism. Herein, we present molecular model compounds, (Ph2N)3V=N-P(O)Ar2 (Ar = C6F5 (2a), Ph (2b)), which are reactive to both weak H atom donors and a Me3Si (a "bulky hydrogen atom" surrogate) donor, 1,4-bis(trimethylsilyl)pyrazine. While the former reaction led to product decomposition, the latter resulted in the isolation of the reduced, silylated complexes (Ph2N)3V-N=P(OSiMe3)Ar2 (3a/b). Detailed analyses of possible reaction pathways, involving the isolation and full characterization of potential stepwise square-scheme intermediates, as well as the determination of minimum experimentally and computationally derived thermochemical values, are described. We find that stepwise electron transfer (ET) + silylium transfer (ST) or concerted EST mechanisms are most likely. This study provides the first experimental evidence supporting a ROA mechanism and may inform future studies in homogeneous or heterogeneous C-H activation chemistry, as well as open up a possible new avenue for main group/transition metal cooperative redox reactivity.

Original languageEnglish
Pages (from-to)15375-15383
Number of pages9
JournalJournal of the American Chemical Society
Volume140
Issue number45
DOIs
StatePublished - 14 Nov 2018

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