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N2O Reductase Activity of a [Cu4S] Cluster in the 4CuI Redox State Modulated by Hydrogen Bond Donors and Proton Relays in the Secondary Coordination Sphere.

N2O Reductase Activity of a [Cu4S] Cluster in the 4CuI Redox State Modulated by Hydrogen Bond Donors and Proton Relays in the Secondary Coordination Sphere.

Authors :
Hsu, Chia‐Wei
Rathnayaka, Suresh C.
Islam, Shahidul M.
MacMillan, Samantha N.
Mankad, Neal P.
Source :
Angewandte Chemie; Jan2020, Vol. 132 Issue 2, p637-641, 5p
Publication Year :
2020

Abstract

The model complex [Cu4(μ4‐S)(dppa)4]2+ (1, dppa=μ2‐(Ph2P)2NH) has N2O reductase activity in methanol solvent, mediating 2 H+/2 e− reduction of N2O to N2+H2O in the presence of an exogenous electron donor (CoCp2). A stoichiometric product with two deprotonated dppa ligands was characterized, indicating a key role of second‐sphere N−H residues as proton donors during N2O reduction. The activity of 1 towards N2O was suppressed in solvents that are unable to provide hydrogen bonding to the second‐sphere N−H groups. Structural and computational data indicate that second‐sphere hydrogen bonding induces structural distortion of the [Cu4S] active site, accessing a strained geometry with enhanced reactivity due to localization of electron density along a dicopper edge site. The behavior of 1 mimics aspects of the CuZ catalytic site of nitrous oxide reductase: activity in the 4CuI:1S redox state, use of a second‐sphere proton donor, and reactivity dependence on both primary and secondary sphere effects. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00448249
Volume :
132
Issue :
2
Database :
Complementary Index
Journal :
Angewandte Chemie
Publication Type :
Academic Journal
Accession number :
141002522
Full Text :
https://doi.org/10.1002/ange.201906327