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Article Abstract
Herein, we investigate the proton-coupled electron transfer (PCET) reactivity of a cobalt(I) complex with a proton-responsive pyridin-4-ol PNP pincer-type ligand (HL = 2,6-bis((bis--butylphosphaneyl)-methyl)pyridin-4-ol). The cobalt(II) complexes [(L)CoCl], , and [(L)Co(MeCN)], , with the deprotonated ligand and [(HL)Co(MeCN)], , with the protonated ligand, were synthesized and characterized. has a p of 18 ± 1, and the reduction of appears at -1.08 V vs. FeCp in MeCN. This leads to a bond dissociation free energy (BDFE) of the OH bond in [(HL)Co(MeCN)], , of 52 kcal mol, which is supported by DFT calculations. The solution BDFE of equals the BDFE of / H, and indeed, slowly loses dihydrogen. Kinetic analysis revealed a first-order rate law in with a reaction rate constant of 3.2 × 10 s at 25 °C and a positive activation entropy Δ of 9.4 ± 0.6 cal (Δ = 24.3 ± 0.2 kcal mol) for H loss. Based on these kinetic results, H/D labeling studies, and DFT calculations, a unimolecular mechanism is proposed. However, H atom transfer from to acceptors such as (2,2,6,6-tetramethylpiperidin-1-yl)oxyl or 2,4,6--butylphenoxide is very fast ( of 10 s M for the reaction of with TEMPO) and H loss can be easily outcompeted.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC12284867 | PMC |
| http://dx.doi.org/10.1021/acs.inorgchem.5c01792 | DOI Listing |
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