In:
Angewandte Chemie International Edition, Wiley, Vol. 59, No. 2 ( 2020-01-07), p. 627-631
Kurzfassung:
The model complex [Cu 4 (μ 4 ‐S)(dppa) 4 ] 2+ ( 1 , dppa=μ 2 ‐(Ph 2 P) 2 NH) has N 2 O reductase activity in methanol solvent, mediating 2 H + /2 e − reduction of N 2 O to N 2 +H 2 O in the presence of an exogenous electron donor (CoCp 2 ). A stoichiometric product with two deprotonated dppa ligands was characterized, indicating a key role of second‐sphere N−H residues as proton donors during N 2 O reduction. The activity of 1 towards N 2 O 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 [Cu 4 S] 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 Cu Z catalytic site of nitrous oxide reductase: activity in the 4Cu I :1S redox state, use of a second‐sphere proton donor, and reactivity dependence on both primary and secondary sphere effects.
Materialart:
Online-Ressource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.201906327
Sprache:
Englisch
Verlag:
Wiley
Publikationsdatum:
2020
ZDB Id:
2011836-3
ZDB Id:
123227-7