Abstract
AbstractProton‐coupled electron transfer (PCET) events play a key role in countless chemical transformations, but they come in many physical variants which are hard to distinguish experimentally. While present theoretical approaches to treat these events are mostly based on physical rate coefficient models of various complexity, it is now argued that it is both feasible and fruitful to directly analyze the electronic N‐electron wavefunctions of these processes along their intrinsic reaction coordinate (IRC). In particular, for model systems of lipoxygenase and the high‐valent oxoiron(IV) intermediate TauD‐J it is shown that by invoking the intrinsic bond orbital (IBO) representation of the wavefunction, the common boundary cases of hydrogen atom transfer (HAT) and concerted PCET (cPCET) can be directly and unambiguously distinguished in a straightforward manner.
Highlights
The transfer of a net hydrogen atom as part of a chemical reaction can proceed in many different ways
Reactions in which electron and proton travel together as a true hydrogen atom will be called hydrogen atom transfer (HAT); the more general term concerted PCET (cPCET) will be used only when proton and electron are transferred in concert, but do not travel together, a definition similar to the one used by Shaik and co-workers.[7a]. Scheme 1 shows two representative cases, which we will discuss in detail below
We have previously demonstrated that the changes which intrinsic bond orbital (IBO) undergo along a given reaction path can be linked to curly arrows[9] and are suitable for the investigation of C(sp3)ÀH activation reactions.[10]
Summary
The transfer of a net hydrogen atom as part of a chemical reaction can proceed in many different ways. Representation of the electron flow in HAT and cPCET events from C(sp3)ÀH bonds to an acceptor (FeIV=O or FeIIIÀOH).
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