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Kinetic Isotope Effect Determination Probes the Spin of the Transition State, Its Stereochemistry, and Its Ligand Sphere in Hydrogen Abstraction Reactions of Oxoiron(IV) Complexes
Accounts of Chemical Research ( IF 20.955 ) Pub Date : 2018-01-03 , DOI: 10.1021/acs.accounts.7b00442
Debasish Mandal, Dibyendu Mallick, Sason Shaik

Since tunneling “cuts through” barriers, it serves as a chemical selectivity factor. Thus, we show that in a family of oxoirons reacting with one hydrocarbon, the tunneling efficiency increases as the ligands become better electron donors. This generates counterintuitive-reactivity patterns, like antielectrophilic reactivity, and induces spin-state reactivity reversals because of differing steric demands of the corresponding 2S+1TS species, etc. Finally, for the same series, the Account reaches intuitive understanding of tunneling trends. It is shown that the increase of ligand’s donicity results in electrostatic narrowing of the barrier, while the decrease of donicity and increase of bond-order asymmetry in the TS (inter alia due to Bell–Evans–Polanyi effects) broadens the barrier. Predictions are made that usage of powerful electron-donating ligands may train H-abstractors to activate the strongest C–H bond in a molecule. The concepts developed here are likely to be applicable to other oxometals in the d- and f-blocks.
更新日期:2018-01-06

 

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