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Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer?

ABSTRACT: In a possibly biomimetic fashion, formally copper(III)-oxygen complexes LCu(III)-OH (1) and LCu(III)-OOCm (2) (L2- = N,N'-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide, Cm = ?,?-dimethylbenzyl) have been shown to activate X-H bonds (X = C, O). Herein, we demonstrate similar X-H bond activation by a formally Cu(III) complex supported by the same dicarboxamido ligand, LCu(III)-O2CAr1 (3, Ar1 = meta-chlorophenyl), and we compare its reactivity to that of 1 and 2. Kinetic measurements revealed a second order reaction with distinct differences in the rates: 1 reacts the fastest in the presence of O-H or C-H based substrates, followed by 3, which is followed by (unreactive) 2. The difference in reactivity is attributed to both a varying oxidizing ability of the studied complexes and to a variation in X-H bond functionalization mechanisms, which in these cases are characterized as either a hydrogen-atom transfer (HAT) or a concerted proton-coupled electron transfer (cPCET). Select theoretical tools have been employed to distinguish these two cases, both of which generally focus on whether the electron (e-) and proton (H+) travel "together" as a true H atom, (HAT), or whether the H+ and e- are transferred in concert, but travel between different donor/acceptor centers (cPCET). In this work, we reveal that both mechanisms are active for X-H bond activation by 1-3, with interesting variations as a function of substrate and copper functionality.

SUBMITTER: Mandal M

PROVIDER: S-EPMC7197025 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer?

Mandal Mukunda M Elwell Courtney E CE Bouchey Caitlin J CJ Zerk Timothy J TJ Tolman William B WB Cramer Christopher J CJ

Journal of the American Chemical Society 20191016 43

In a possibly biomimetic fashion, formally copper(III)-oxygen complexes LCu(III)-OH (1) and LCu(III)-OOCm (2) (L2- = N,N'-bis(2,6-diisopropylphenyl)-2,6-pyridinedicarboxamide, Cm = α,α-dimethylbenzyl) have been shown to activate X-H bonds (X = C, O). Herein, we demonstrate similar X-H bond activation by a formally Cu(III) complex supported by the same dicarboxamido ligand, LCu(III)-O2CAr1 (3, Ar1 = meta-chlorop ...[more]

PMID: 31617707

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Project description:The coupling between electrons and protons and the long-range transport of protons play important roles throughout biology. Biomimetic systems derived from benzimidazole-phenol (BIP) constructs have been designed to undergo proton-coupled electron transfer (PCET) upon electrochemical or photochemical oxidation. Moreover, these systems can transport protons along hydrogen-bonded networks or proton wires through multiproton PCET. Herein, the nonequilibrium dynamics of both single and double proton transfer in BIP molecules initiated by oxidation are investigated with first-principles molecular dynamics simulations. Although these processes are concerted in that no thermodynamically stable intermediate is observed, the simulations predict that they are predominantly asynchronous on the ultrafast time scale. For both systems, the first proton transfer typically occurs ∼100 fs after electron transfer. For the double proton transfer system, typically the second proton transfer occurs hundreds of femtoseconds after the initial proton transfer. A machine learning algorithm was used to identify the key molecular vibrational modes essential for proton transfer: a slow, in-plane bending mode that dominates the overall inner-sphere reorganization, the proton donor-acceptor motion that leads to vibrational coherence, and the faster donor-hydrogen stretching mode. The asynchronous double proton transfer mechanism can be understood in terms of a significant mode corresponding to the two anticorrelated proton donor-acceptor motions, typically decreasing only one donor-acceptor distance at a time. Although these PCET processes appear concerted on the time scale of typical electrochemical experiments, attaching these BIP constructs to photosensitizers may enable the detection of the asynchronicity of the electron and multiple proton transfers with ultrafast two-dimensional spectroscopy. Understanding the fundamental PCET mechanisms at this level will guide the design of PCET systems for catalysis and energy conversion processes.

Dataset Information

Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer?

Publications

Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer?

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