ja6b05480_si_002.cif (1.26 MB)
A One-Hole Cu4S Cluster with N2O Reductase Activity: A Structural and Functional Model for CuZ*
dataset
posted on 2016-09-29, 00:00 authored by Brittany
J. Johnson, William E. Antholine, Sergey V. Lindeman, Michael J. Graham, Neal P. MankadDuring
bacterial denitrification, two-electron reduction of N2O occurs at a [Cu4(μ4-S)] catalytic
site (CuZ*) embedded within the nitrous oxide reductase
(N2OR) enzyme. In this Communication, an amidinate-supported
[Cu4(μ4-S)] model cluster in its one-hole
(S = 1/2) redox state is thoroughly
characterized. Along with its two-hole redox partner and fully reduced
clusters reported previously, the new species completes the two-electron
redox series of [Cu4(μ4-S)] model complexes
with catalytically relevant oxidation states for the first time. More
importantly, N2O is reduced by the one-hole cluster to
produce N2 and the two-hole cluster, thereby completing
a closed cycle for N2O reduction. Not only is the title
complex thus the best structural model for CuZ* to date,
but it also serves as a functional CuZ* mimic.