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

Hsu, Chia‐Wei; Rathnayaka, Suresh C.; Islam, Shahidul; MacMillan, Samantha N.; Mankad, Neal P.

doi:10.1002/ange.201906327

Cited by 6 publications

(4 citation statements)

References 31 publications

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“…In a recent work by Mankad, ligands of dppa (μ 2 -(Ph 2 P) 2 NH) with potential proton delivery capability were designed in the preparation of the [Cu 4 (μ 4 -S)(dppa) 4 ] 2+ cluster. 446 The model cluster exhibited N 2 O reductase activity in the presence of hydrogen bond molecules such as methanol, while its catalytic activity was heavily suppressed in solvents without hydrogen bonding sites. Mechanism studies from both structural and computational data suggested that the second-sphere hydrogen bonding induced structural distortion of the [Cu 4 S] active site, therefore enhancing the ability of binding and activating N 2 O.…”

Section: Activating Substrates Bymentioning

confidence: 99%

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

et al. 2022

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The surface and interface coordination structures of heterogeneous metal catalysts are crucial to their catalytic performance. However, the complicated surface and interface structures of heterogeneous catalysts make it challenging to identify the molecular-level structure of their active sites and thus precisely control their performance. To address this challenge, atomically dispersed metal catalysts (ADMCs) and ligand-protected atomically precise metal clusters (APMCs) have been emerging as two important classes of model heterogeneous catalysts in recent years, helping to build bridge between homogeneous and heterogeneous catalysis. This review illustrates how the surface and interface coordination chemistry of these two types of model catalysts determines the catalytic performance from multiple dimensions. The section of ADMCs starts with the local coordination structure of metal sites at the metal–support interface, and then focuses on the effects of coordinating atoms, including their basicity and hardness/softness. Studies are also summarized to discuss the cooperativity achieved by dual metal sites and remote effects. In the section of APMCs, the roles of surface ligands and supports in determining the catalytic activity, selectivity, and stability of APMCs are illustrated. Finally, some personal perspectives on the further development of surface coordination and interface chemistry for model heterogeneous metal catalysts are presented.

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Section: Activating Substrates Bymentioning

confidence: 99%

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

et al. 2022

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“…12,13 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. 14,15 Somewhat earlier, the Tolman laboratory reported a mixedvalent tricopper compound featuring a disulfide ligand in a μ 3η 2 ,η 1 -S,η 1 ,S′ bridging motif that was also competent to reduce N 2 O to N 2 (Figure 2b). 16 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%

“…14,132.20,128.78,125.76,125.15,122.11,54.46,42.59. 2,8,3.1.1 3,7 .1 9,13 ]heneicosa-1-( 19), 3,5,7(21), 9,11,13(20), 15,6,12,18-Tris(Nmethylamine), 10, and 2,8,14,15-Tetrathiatetracyclo-[14.3.1.1 3,7 .1 9,13 ]docosa-1 (20), 3,5,7(22), 9,11,13(21),16,18nonaene, 6,12,19-Tri(N-methylamine)-, 11. A portion of 2-(methylamino)benzenethiol was dissolved in MeCN and stirred overnight in the open air to produce 2,2′-disulfanediylbis(N-methylaniline), 9.…”

Section: ■ Introductionmentioning

confidence: 99%

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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“…Mankad reported several [Cu clusters which have N 2 O reductase activities, opening the door for these bioinspired Cu clusters to their practical application in the conversion of greenhouse gases. 13,14 In addition, the known Cu clusters usually consist of Cu I centers which are generally sensitive to oxidation, making them easily agglomeration and deactivate during the catalytic process. 15 Thus, the catalytic potential of most Cu clusters has been severely limited by their low stabilities.…”

mentioning

confidence: 99%

Biomimetic Cu₄ Cluster Encapsulated within Hollow Titanium-Oxo Nanoring for Electrochemical CO₂ Reduction to Ethylene

Fan

Cheng

Qiu

et al. 2023

ACS Materials Lett.

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The construction of biomimetic cluster catalysts with metalloenzyme-like active sites may open an avenue for the challenging transformation of greenhouse gases (e.g., CO 2 ) to high-value chemicals. Cu-enzymes occur in all three biological kingdoms, with Cu Z clusters serving as representative reaction sites that catalyze challenging transformations. However, artificial Cu clusters with analogous Cu Z structures and high stability are still rare. In this work, we have successfully adopted a Ti 9 -oxo nanoring as an inorganic templating scaffold to isolate a small Cu 4 cluster, which can be regarded as a atomically precise bioinspired cluster with metalloenzyme-like catalytic sites (Cu Z ). Importantly, Cu 4 @Ti 9 displays high selectivity for the electrocatalytic reduction of CO 2 to C 2 H 4 (FE: 47.6 ± 3.4%) at 400 mA cm −2 and good catalytic durability (8 h). The bioinspired Cu 4 @Ti 9 not only represents the first example of Cu cluster directly encapsulated by a metal-oxo shell but also opens the CO 2 electroreduction to ethylene applications of atomically precise metallic clusters.

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

Cited by 6 publications

References 31 publications

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

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

Biomimetic Cu₄ Cluster Encapsulated within Hollow Titanium-Oxo Nanoring for Electrochemical CO₂ Reduction to Ethylene

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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

Cited by 6 publications

References 31 publications

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

Surface and Interface Coordination Chemistry Learned from Model Heterogeneous Metal Nanocatalysts: From Atomically Dispersed Catalysts to Atomically Precise Clusters

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

Biomimetic Cu4 Cluster Encapsulated within Hollow Titanium-Oxo Nanoring for Electrochemical CO2 Reduction to Ethylene

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

Biomimetic Cu₄ Cluster Encapsulated within Hollow Titanium-Oxo Nanoring for Electrochemical CO₂ Reduction to Ethylene