A 5000-fold Increase in the HAT Reactivity of a Nonheme FeIV=O Complex Simply by Replacing Two Pyridines of N4Py Ligand with Pyrazoles

Abstract

A pentadentate [N5] ligand (N2Py2Pz) based on the classic N4Py (N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework has been synthesized by replacing the two pyridylmethyl arms with corresponding (N-methyl)pyrazolylmethyl units to form [N-bis(1-methyl-2-pyrazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L1). The oxidation of the iron(II) precursor (N2Py2Pz)FeII(OTf)2 (1) with (tBuSO2)C6H4IO at 298 K leads to the formation of the [FeIV(O)(N2Py2Pz)]2+ intermediate (2) with a near-IR band at 750 nm (εM = 250 M−1cm−1) and a t1/2 ~ 2 min at 298 K. The introduction of the less basic pyrazolylmethyl ligands in place of two pyridylmethyl units generates FeIV=O intermediate 2 that exhibits a cyclohexane oxidation rate of 0.29 s−1 at 298 K, which is 5,000-fold faster than that observed for the classic FeIV(O)N4Py parent complex and 40,000-fold more reactive than the least reactive FeIV(O)N2Py2Q′ complex in this series (Py = pyridine, Q′ = isoquinoline) recently reported by Nordlander