Coordination chemistry of the CuZ site in nitrous oxide reductase and its synthetic mimics

Rathnayaka, Suresh C.; Mankad, Neal P.

doi:10.1016/j.ccr.2020.213718

Cited by 17 publications

(14 citation statements)

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“…2a), there has been great interest in designing synthetic multicopper platforms for N 2 O activation. [67][68][69] In 2014, Torelli and coworkers reported the preparation and characterization of a dinuclear complex 37a containing a mixed-valent [Cu 2 (µ-SR)] Scheme 35 Activation of CO 2 by a bimetallic Yb complex.…”

Section: Biomimetic Multicopper Complexesmentioning

confidence: 99%

“…2a), there has been great interest in designing synthetic multicopper platforms for N 2 O activation. 67–69 In 2014, Torelli and coworkers reported the preparation and characterization of a dinuclear complex 37a containing a mixed-valent [Cu 2 (μ-SR)] core and studied its reactivity towards N 2 O reduction (Scheme 37). 70 This thiolate-bridged dicopper( i , ii ) cluster was found to reduce N 2 O to N 2 , resulting in fully oxidized Cu( ii ) metal centers with a double bridged [Cu II 2 (μ-SR)(μ-OH)] core ( 37b ).…”

Section: Bimetallic N2o Activationmentioning

confidence: 99%

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Recent advances in cooperative activation of CO₂and N₂O by bimetallic coordination complexes or binuclear reaction pathways

2022

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Section: Biomimetic Multicopper Complexesmentioning

confidence: 99%

Section: Bimetallic N2o Activationmentioning

confidence: 99%

Recent advances in cooperative activation of CO₂and N₂O by bimetallic coordination complexes or binuclear reaction pathways

2022

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“…A model system devised by Mankad and co-workers (Figure a) with mesityl-substituted formamidinate supporting ligands incorporates the Cu 4 (μ 4 -S) core and, despite not being reducible to the all-cuprous state, has been reported to support a N 2 O-to-N 2 turnover. , A topologically similar Cu 4 S compound with charge-neutral, amine-bridged bis (phosphine) ligands has also been described as supporting N 2 O reduction but without preservation of the Cu 4 S core composition. , Somewhat earlier, the Tolman laboratory reported a mixed-valent tricopper compound featuring a disulfide ligand in a μ 3 -η 2 ,η 1 -S,η 1 ,S′ bridging motif that was also competent to reduce N 2 O to N 2 (Figure b) . Other small-molecule copper complexes that have been devised as N 2 O active site models have been reviewed by Mankad …”

Section: Introductionmentioning

confidence: 99%

“…16 Other small-molecule copper complexes that have been devised as N 2 O active site models have been reviewed by Mankad. 17 In 2003, a brief report by Henkel and co-workers related the preparation and structure of a pair of charge-neutral tetracuprous compounds supported by tetradentate diamino bis(thiolate) (L-N R 2 S 2 (2−)) ligands (Figure 2c) but with no attending account of their reactivity. 18 Considering their fully reduced state, these compounds appeared plausible as candidates to a Cu 2 I Cu 2 II (μ 4 -S) model compound by direct S atom addition.…”

Section: ■ Introductionmentioning

confidence: 99%

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Fully Reduced and Mixed-Valent Multi-Copper Aggregates Supported by Tetradentate Diamino Bis(thiolate) Ligands

Wang,

Barnes,

Ferrara

et al. 2023

Inorg. Chem.

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Tetradentate diamino bis(thiolate) ligands (L-N 2 S 2 (2−)) with saturated linkages between heteroatoms support fully reduced [(Cu(L-N 2 S 2 )) 2 Cu 2 ] complexes that bear relevance as an entry point toward molecules featuring the Cu 2 I Cu 2 II (μ 4 -S) core composition of nitrous oxide reductase (N 2 OR). Tetracopper [(Cu(L-N 2 (S Me 2 ) 2 )) 2 Cu 2 ] (L-N 2 (S Me 2 H) 2 = N 1 ,N 2 -bis(2-methyl-2mercaptopropane)-N 1 ,N 2 -dimethylethane-1,2-diamine) does not support clean S atom oxidative addition but undergoes Cl atom transfer from PhICl 2 or Ph 3 CCl to afford [(Cu(L-N 2 (S Me 2 ) 2 )) 3 (CuCl) 5 ], 14. When introduced to Cu(I) sources, the L-N 2 (S Ar H) 2 ligand (L-N 2 (S Ar H) 2 = N 1 ,N 2 -bis(2-mercaptophenyl)-N 1 ,N 2 -dimethylethane-1,2-diamine), made by a newly devised route from N 1 ,N 2 -bis(2fluorophenyl)-N 1 ,N 2 -dimethylethane-1,2-diamine, ultimately yields the mixed-valent pentacopper [(Cu(L-N 2 S Ar 2 )) 3 Cu 2 ] (19), which has 3-fold rotational symmetry (D 3 ) around a Cu 2 axis. The single Cu II ion of 19 is ensconced within an equatorial L-N 2 (S Ar ) 2 (2−) ligand, as shown by 14 N coupling in its EPR spectrum. Formation of 19 proceeds from an initial, fully reduced product, [(Cu(L-N 2 S Ar 2 )) 3 Cu 2 (Cu(MeCN))] (17), which is C 2 symmetric and exceedingly air-sensitive. While unreactive toward chalcogen donors, 19 supports reversible reduction to the all-cuprous state; generation of [19] 1− and treatment with S atom donors only return 19 because structural adjustments necessary for oxidative addition are noncompetitive with outer-sphere electron transfer. Oxidation of 19 is marked by intense darkening, consistent with greater mixed valency, and by dimerization in the crystalline state to a decacopper species ([20] 2+ ) of S 4 symmetry.

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Photocatalytic Removal of the Greenhouse Gas Nitrous Oxide by Liposomal Microreactors

et al. 2022

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Nitrous oxide (N 2 O) is a potent greenhouse and ozone-reactive gas for which emissions are growing rapidly due to increasingly intensive agriculture. Synthetic catalysts for N 2 O decomposition typically contain precious metals and/or operate at elevated temperatures driving a desire for more sustainable alternatives. Here we demonstrate self-assembly of liposomal microreactors enabling catalytic reduction of N 2 O to the climate neutral product N 2 . Photoexcitation of graphitic Ndoped carbon dots delivers electrons to encapsulated N 2 O Reductase enzymes via a lipid-soluble biomolecular wire provided by the MtrCAB protein complex. Within the microreactor, electron transfer from MtrCAB to N 2 O Reductase is facilitated by the general redox mediator methyl viologen. The liposomal microreactors use only earth-abundant elements to catalyze N 2 O removal in ambient, aqueous conditions.

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Coordination chemistry of the CuZ site in nitrous oxide reductase and its synthetic mimics

Cited by 17 publications

References 83 publications

Recent advances in cooperative activation of CO₂and N₂O by bimetallic coordination complexes or binuclear reaction pathways

Recent advances in cooperative activation of CO₂and N₂O by bimetallic coordination complexes or binuclear reaction pathways

Fully Reduced and Mixed-Valent Multi-Copper Aggregates Supported by Tetradentate Diamino Bis(thiolate) Ligands

Photocatalytic Removal of the Greenhouse Gas Nitrous Oxide by Liposomal Microreactors

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Coordination chemistry of the CuZ site in nitrous oxide reductase and its synthetic mimics

Cited by 17 publications

References 83 publications

Recent advances in cooperative activation of CO2and N2O by bimetallic coordination complexes or binuclear reaction pathways

Recent advances in cooperative activation of CO2and N2O by bimetallic coordination complexes or binuclear reaction pathways

Fully Reduced and Mixed-Valent Multi-Copper Aggregates Supported by Tetradentate Diamino Bis(thiolate) Ligands

Photocatalytic Removal of the Greenhouse Gas Nitrous Oxide by Liposomal Microreactors

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Product

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Recent advances in cooperative activation of CO₂and N₂O by bimetallic coordination complexes or binuclear reaction pathways

Recent advances in cooperative activation of CO₂and N₂O by bimetallic coordination complexes or binuclear reaction pathways