A One-Hole Cu4S Cluster with N2O Reductase Activity: A Structural and Functional Model for CuZ.
During 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 N2and 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.
Department of Chemistry, University of Illinois at Chicago , 845 West Taylor Street, Chicago, Illinois 60607, United States.
Brittany J
BJ
Johnson
Department of Biophysics, Medical College of Wisconsin , 8701 Watertown Plank Road, Milwaukee, Wisconsin 53226, United States.
William E
WE
Antholine
Department of Chemistry, Marquette University , 535 North 14th Street, Milwaukee, Wisconsin 53201, United States.
Sergey V
SV
Lindeman
Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Michael J
MJ
Graham
Department of Chemistry, University of Illinois at Chicago , 845 West Taylor Street, Chicago, Illinois 60607, United States.
Neal P
NP
Mankad
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