Sulfur Ligand Substitution at the Nickel(II) Sites of Cubane-Type and Cubanoid NiFe<sub>3</sub>S<sub>4</sub> Clusters Relevant to the C-Clusters of Carbon Monoxide Dehydrogenase

Sun, Jibin; Tessier, Christian; Holm, R. H.

doi:10.1021/ic062362z

Cited by 54 publications

(43 citation statements)

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“…If CO 2 (and its mimics) indeed bind to the S = 1 = 2 C red1 state, it should be possible to probe that binding further by searching for 13 C hyperfine interactions by using ENDOR or ESEEM spectroscopy. The electronic structure of C red2 remains poorly understood, and future efforts should be placed at preparing site-directed mutants in which the B-cluster is either absent or not reducible.…”

Section: Methodsmentioning

confidence: 99%

“…[15] related synthetic clusters have been studied by Münck, Holm, et al, who found that such clusters can exist in states ranging from all-ferrous to all-ferric. [12,13] The electronic configuration of C red2 is uncertain because of overlap of C red2 and reduced Bcluster Mössbauer features, as well as weak magnetic interactions between C red2 and the reduced B-cluster. C red2 should be 2 electrons more reduced than C red1 , but where those electrons localize on the C-cluster is unknown.…”

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confidence: 99%

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Implications of a Carboxylate‐Bound C‐Cluster Structure of Carbon Monoxide Dehydrogenase

Lindahl¹

2008

Angew Chem Int Ed

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bioinorganic chemistry · carbon dioxide fixation · enzyme catalysis · metalloenzymes · nickel Nickel-containing carbon monoxide dehydrogenases (CODHs) catalyze the reversible reduction of CO 2 to CO [Eq. (1)]. They are found in anaerobicbacteria and archaea that grow chemoautotrophically on simple carbon sources.[1] These organisms play a major role in the global carbon cycle [2] and are among the most evolutionarily primitive forms of life.[3] The enzymes from Rhodospirillium rubrum (CODH Rr ) and Carboxydothermus hydrogenoformans (CODH Ch II) are monofunctional b 2 homodimers. Acetyl-CoA synthase/carbon monoxide dehydrogenase from Moorella thermoacetica (ACS/CODH Mt ) is a bifunctional a 2 b 2 tetramer that also catalyzes the synthesis of acetyl-CoA. Its b 2 subunits are homologous to the monofunctional CODH b 2 homodimers.Each b subunit contains the active site responsible for the reaction of Equation (1), known as the Ccluster, as well as an Fe 4 S 4 B-cluster. Another Fe 4 S 4 cluster (the D-cluster) bridges the two b subunits. Band D-clusters transfer electrons between the Ccluster and external redox agents. The structures of the C-cluster from CODH Ch II and ACS/CODH Mt have been determined through X-ray crystallography to high resolution (Figure 1 a). [4][5][6] The structure of the C-cluster from ACS/CODH Mt is essentially identical except for the absence of the m 2 -bridging sulfide ligand. This difference has prompted a controversy regarding the mechanistic role of this ion. Dobbek et al. concluded that a sulfide ligand is required for catalytic activity and found that incubation under CO (the conditions used in crystallizing ACS/CODH Mt ) eliminated the sulfide ion from the C-cluster and inactivated the enzyme.[7] By adding sulfide ion to CODH Rr and ACS/CODH Mt , Feng and Lindahl found precisely the opposite, namely that sulfide inhibited catalysis and that CODH is not inactivated by CO.

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Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

Implications of a Carboxylate‐Bound C‐Cluster Structure of Carbon Monoxide Dehydrogenase

Lindahl¹

2008

Angew Chem Int Ed

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“…Further, the approximately planar Ni sites in intermediate (b) and the cyanide-ligated C-clusters (c) and (d) (Figure 1) are approached in clusters such as [(tdt)NiFe 3 S 4 (LS 3 )] 3− . This and related cubanoid clusters are produced by phosphine substitution with a strong in-plane chelating ligand and attendant rupture of the axial Ni-(µ 3 -S) bond 16,17. However, key attributes of the C-cluster have not been experimentally attained.…”

Section: Introductionmentioning

confidence: 99%

Reactions of the Terminal Ni^II−OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular Ni^II···Fe^IIBridged Site

2010

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A singular feature of the catalytic C-cluster of carbon monoxide dehydrogenase is a sulfide-bridged Ni⋯Fe locus where substrate is bound and transformed in the reversible reaction CO + H2O ⇌ CO2 + 2H+ + 2e−. A similar structure has been sought in this work. Mononuclear planar NiII complexes [Ni(pyN2Me2)L]1− (pyN2Me2 = bis(2,6-dimethylphenyl)-2,6-pyridinedicarboxamidate(2-)) derived from a NNN pincer ligand have been prepared including L = OH− (1) and CN− (7). Complex 1 reacts with ethyl formate and CO2 to form unidentate L = HCO2− (5) and HCO3− (6) products. A binucleating macrocycle was prepared which specifically binds NiII at a NNN pincer site and five-coordinate FeII at a triamine site. The NiII macrocyle forms hydroxo (14) and cyanide complexes (15) analogous to 1 and 7. Reaction of 14 with FeCl2 alone and with ethyl formate and 15 with FeCl2 affords molecules with the NiII-L-FeII bridge unit in which L = µ2:η1-OH− (17) and µ2:η2-HCO2− (18) and -CN− (19). All bridges are non-linear (17, 140.0°; 18, M-O-C 135.9° (Ni), 120.2° (Fe); 19, Ni-C-N 170.3°, Fe-N-C 141.8°) with Ni⋯Fe separations of 3.7–4.8 Å. The NiIIFeII complexes, lacking appropriate Ni-Fe-S cluster structures, are not site analogues but their synthesis and reactivity provide the first demonstration that molecular NiII…FeII sites and bridges can be attained, a necessity in the biomimetic chemistry of C-clusters.

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“…With respect to the anaerobic CODHs, attempts to mimic the spectroscopic properties of the NiFeS active site with synthetic complexes were underway even before the determination of the active site structure. There have been two major approaches: construction of [NiFe 3 S 4 ] clusters, spearheaded largely by the Holm group [151][152][153][154][155], and efforts to make heterobimetallic [NiFe] complexes, research closely related to the modeling of [NiFe]-hydrogenases (see Sect. 3).…”

Section: Structural Models Of Codhsmentioning

confidence: 99%

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

Jennings

Laureanti

Jones

2015

Homo- And Heterobimetallic Complexes in Catalysis

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The active sites of several bioenergetically important metalloenzymes that perform multielectron redox reactions feature heterobimetallic complexes. Herein, we review recent understanding of the structure and mechanisms of hydrogenases, formate dehydrogenases, and carbon monoxide dehydrogenases. Then we evaluate progress toward creating functional, small-molecule complexes that reproduce the activities of these active sites. Particular emphasis is placed on comparing catalytic properties including turnover number, turnover frequency, required overpotential, and catalyst stability. Opportunities and challenges for future work are also considered.

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Sulfur Ligand Substitution at the Nickel(II) Sites of Cubane-Type and Cubanoid NiFe₃S₄ Clusters Relevant to the C-Clusters of Carbon Monoxide Dehydrogenase

Cited by 54 publications

References 46 publications

Implications of a Carboxylate‐Bound C‐Cluster Structure of Carbon Monoxide Dehydrogenase

Implications of a Carboxylate‐Bound C‐Cluster Structure of Carbon Monoxide Dehydrogenase

Reactions of the Terminal Ni^II−OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular Ni^II···Fe^IIBridged Site

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

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Sulfur Ligand Substitution at the Nickel(II) Sites of Cubane-Type and Cubanoid NiFe3S4 Clusters Relevant to the C-Clusters of Carbon Monoxide Dehydrogenase

Cited by 54 publications

References 46 publications

Implications of a Carboxylate‐Bound C‐Cluster Structure of Carbon Monoxide Dehydrogenase

Implications of a Carboxylate‐Bound C‐Cluster Structure of Carbon Monoxide Dehydrogenase

Reactions of the Terminal NiII−OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular NiII···FeIIBridged Site

Biomimetic Complexes for Production of Dihydrogen and Reduction of CO2

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Product

Resources

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Sulfur Ligand Substitution at the Nickel(II) Sites of Cubane-Type and Cubanoid NiFe₃S₄ Clusters Relevant to the C-Clusters of Carbon Monoxide Dehydrogenase

Reactions of the Terminal Ni^II−OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular Ni^II···Fe^IIBridged Site