Privileged Role of Thiolate as the Axial Ligand in Hydrogen Atom Transfer Reactions by Oxoiron(IV) Complexes in Shaping the Potential Energy Surface and Inducing Significant H‑Atom Tunneling

Privileged Role of Thiolate as the Axial Ligand in Hydrogen Atom Transfer Reactions by Oxoiron(IV) Complexes in Shaping the Potential Energy Surface and Inducing Significant H‑Atom Tunneling

An H/D kinetic isotope effect (KIE) of 80 is found at −20 °C for the oxidation of 9,10-dihydro­anthracene by [FeIV(O)­(TMCS)]+, a complex supported by the tetramethylcyclam (TMC) macrocycle with a tethered thiolate. This KIE value approaches that previously predicted by DFT calculations. Other [FeIV...

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Veröffentlicht in:Journal of the American Chemical Society 2017-12, Vol.139 (51), p.18705-18713
Hauptverfasser: Klein, Johannes E. M. N, Mandal, Debasish, Ching, Wei-Min, Mallick, Dibyendu, Que, Lawrence, Shaik, Sason
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container_end_page 18713
container_issue 51
container_start_page 18705
container_title Journal of the American Chemical Society
container_volume 139
creator Klein, Johannes E. M. N
Mandal, Debasish
Ching, Wei-Min
Mallick, Dibyendu
Que, Lawrence
Shaik, Sason
description An H/D kinetic isotope effect (KIE) of 80 is found at −20 °C for the oxidation of 9,10-dihydro­anthracene by [FeIV(O)­(TMCS)]+, a complex supported by the tetramethylcyclam (TMC) macrocycle with a tethered thiolate. This KIE value approaches that previously predicted by DFT calculations. Other [FeIV(O)­(TMC)­(anion)] complexes exhibit values of 20, suggesting that the thiolate ligand of [FeIV(O)­(TMCS)]+ plays a unique role in facilitating tunneling. Calculations show that tunneling is most enhanced (a) when the bond asymmetry between C–H bond breaking and O–H bond formation in the transition state is minimized, and (b) when the electrostatic interactions in the O---H---C moiety are maximal. These two factorswhich peak for the best electron donor, the thiolate ligandafford a slim and narrow barrier through which the H-atom can tunnel most effectively.
doi_str_mv 10.1021/jacs.7b11300
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