Spectroscopic and Reactivity Comparisons of a Pair of BTAML Complexes with Fe═O and Fe═O Units

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2017 May 9

PMID 28481521

Citations 15

Authors

Santanu Pattanayak

Andrew J Jasniewski

Atanu Rana

Apparao Draksharapu

Kundan K Singh

Andrew Weitz

Michael Hendrich

Lawrence Que Jr

Abhishek Dey

Sayam Sen Gupta

Affiliations

Soon will be listed here.

Abstract

In this report we compare the geometric and electronic structures and reactivities of [Fe(O)] and [Fe(O)] species supported by the same ancillary nonheme biuret tetraamido macrocyclic ligand (bTAML). Resonance Raman studies show that the Fe═O vibration of the [Fe(O)] complex 2 is at 798 cm, compared to 862 cm for the corresponding [Fe(O)] species 3, a 64 cm frequency difference reasonably reproduced by density functional theory calculations. These values are, respectively, the lowest and the highest frequencies observed thus far for nonheme high-valent Fe═O complexes. Extended X-ray absorption fine structure analysis of 3 reveals an Fe═O bond length of 1.59 Å, which is 0.05 Å shorter than that found in complex 2. The redox potentials of 2 and 3 are 0.44 V (measured at pH 12) and 1.19 V (measured at pH 7) versus normal hydrogen electrode, respectively, corresponding to the [Fe(O)]/[Fe(OH)] and [Fe(O)]/[Fe(O)] couples. Consistent with its higher potential (even after correcting for the pH difference), 3 oxidizes benzyl alcohol at pH 7 with a second-order rate constant that is 2500-fold bigger than that for 2 at pH 12. Furthermore, 2 exhibits a classical kinteic isotope effect (KIE) of 3 in the oxidation of benzyl alcohol to benzaldehyde versus a nonclassical KIE of 12 for 3, emphasizing the reactivity differences between 2 and 3.

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