Rebound or Cage Escape? The Role of the Rebound Barrier for the Reactivity of Non-Heme High-Valent FeIV=O species

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dc.contributor.authorKumar, R
dc.contributor.authorAnsari, A
dc.contributor.authorComba, P
dc.date.accessioned2024-10-09T06:35:31Z
dc.date.available2024-10-09T06:35:31Z
dc.date.issued2023
dc.description.abstractOwing to their high reactivity and selectivity, variations in the spin ground state and a range of possible pathways, high-valent FeIV=O species are popular models with potential bioinspired applications. An interesting example of a structure–reactivity pattern is the detailed study with five nonheme amine-pyridine pentadentate ligand FeIV=O species, including N4py: [(L1 )FeIV= O]2+ (1), bntpen: [(L2 )FeIV=O]2+ (2), py2tacn: [(L3 )FeIV=O]2+ (3), and two isomeric bispidine derivatives: [(L4 )FeIV=O]2+ (4) and [(L5 )FeIV=O]2+ (5). In this set, the order of increasing reactivity in the hydroxylation of cyclohexane differs from that with cyclohexadiene as substrate. A comprehensive DFT, ab initio CASSCF/NEVPT2 and DLPNO-CCSD(T) study is presented to untangle the observed patterns. These are well reproduced when both activation barriers for the C H abstraction and the OH rebound are taken into account. An MO, NBO and deformation energy analysis reveals the importance of π(pyr) ! π*xz(FeIII-OH) electron donation for weakening the FeIII-OH bond and thus reducing the rebound barrier. This requires that pyridine rings are oriented perpendicularly to the FeIII-OH bond and this is a subtle but crucial point in ligand design for non heme iron alkane hydroxylation.en_US
dc.identifier.urihttp://hdl.handle.net/123456789/1609
dc.titleRebound or Cage Escape? The Role of the Rebound Barrier for the Reactivity of Non-Heme High-Valent FeIV=O speciesen_US
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