Inorganic clusters with a [Fe<sub>2</sub>MoOS<sub>3</sub>] core—a functional model for acetylene reduction by nitrogenases

Yoshimoto, Koji; Yatabe, Takeshi; Matsumoto, Takahiro; Tran, Viet Ha; Robertson, Andrew W.; Nakai, Hidetaka; Asazawa, Koichiro; Tanaka, Hiroyuki; Ogo, Seiji

doi:10.1039/c6dt01655c

Cited by 4 publications

(4 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Otsuka and Nakamura et al found that NaBH 4 works as a reductant in the catalytic reduction of phenylacetylene to styrene mediated by [49] − , 205 while Ogo and co-workers reported analogous reductions of C 2 H 2 and phenylacetylene catalyzed by an incomplete cuboidal cluster [Mo(O)Fe 2 S 3 Cl 4 ] 2− in the presence of NaBH 4 as the reducing agent and H 2 O as the proton source. 206 Tanaka and his colleagues employed 49 for electrochemical reduction of C 2 H 2 in a mixed MeOH/THF solution containing LiCl electrolyte. 207 The observed reaction rate was 0.012 mol/(mol cat •min) under the applied voltage at −1.25 V vs SCE and was accelerated to 0.069 mol/(mol cat •min) at 52)), although 49 and 50 were merely dispersed in this medium.…”

Section: Nitrogenase-related Reactions Of Biomimetic Metal−sulfur Clu...mentioning

confidence: 99%

“…Otsuka and Nakamura et al. found that NaBH 4 works as a reductant in the catalytic reduction of phenylacetylene to styrene mediated by [ 49 ] − , while Ogo and co-workers reported analogous reductions of C 2 H 2 and phenylacetylene catalyzed by an incomplete cuboidal cluster [Mo(O)Fe 2 S 3 Cl 4 ] 2– in the presence of NaBH 4 as the reducing agent and H 2 O as the proton source …”

Section: Metal–sulfur Clusters In Nitrogenase-related Chemistrymentioning

confidence: 99%

See 1 more Smart Citation

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

2020

View full text Add to dashboard Cite

Transition metal–sulfur (M–S) compounds are an indispensable means for biological systems to convert N2 into NH3 (biological N2 fixation), and these may have emerged by chemical evolution from a prebiotic N2 fixation system. With a main focus on synthetic species, this article provides a comprehensive review of the chemistry of M–S compounds related to the conversion of N2 and the structures/functions of the nitrogenase cofactors. Three classes of M–S compounds are highlighted here: multinuclear M–S clusters structurally or functionally relevant to the nitrogenase cofactors, mono- and dinuclear transition metal complexes supported by sulfur-containing ligands in N2 and N2H x (x = 2, 4) chemistry, and metal sulfide-based solid materials employed in the reduction of N2. Fair assessments on these classes of compounds revealed that our understanding is still limited in N2 reduction and related substrate reductions. Our aims of this review are to compile a collection of studies performed at atomic to mesoscopic scales and to present potential opportunities for elucidating the roles of metal and sulfur atoms in the biological N2 fixation that might be helpful for the development of functional materials.

show abstract

Section: Nitrogenase-related Reactions Of Biomimetic Metal−sulfur Clu...mentioning

confidence: 99%

Section: Metal–sulfur Clusters In Nitrogenase-related Chemistrymentioning

confidence: 99%

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

2020

View full text Add to dashboard Cite

show abstract

“…Nitrogenases (Nases) are able to reduce nitrogen to ammonia and acetylene to ethylene [ 295 , 296 , 297 , 298 , 299 , 300 , 301 ]. Inorganic Fe/Mo clusters with a [Fe 2 MoOS 3 ] core resemble a part of FeMo-cofactor, the active center of nitrogenases [ 302 ]. The dihydride complex reduced acetylene to ethylene via the vinyl monohydride complex; the detailed mechanism, verified by using various combinations of reductants, substrates, and heavy water, is shown in Figure 25 .…”

Section: Acetylene In Organic Synthesismentioning

confidence: 99%

“…The scale of horizontal axis represents oxidation states 0 to –4, with the initial oxidation state of 1 corresponding to 0. Accordingly, the two and four electron-deprived species correspond to –2 and –4 oxidation states, respectively (reproduced with permission from [ 302 ]. Copyright 2016 the Royal Society of Chemistry.).…”

Section: Figures Schemes and Tablesmentioning

confidence: 99%

Acetylene in Organic Synthesis: Recent Progress and New Uses

et al. 2018

View full text Add to dashboard Cite

Recent progress in the leading synthetic applications of acetylene is discussed from the prospect of rapid development and novel opportunities. A diversity of reactions involving the acetylene molecule to carry out vinylation processes, cross-coupling reactions, synthesis of substituted alkynes, preparation of heterocycles and the construction of a number of functionalized molecules with different levels of molecular complexity were recently studied. Of particular importance is the utilization of acetylene in the synthesis of pharmaceutical substances and drugs. The increasing interest in acetylene and its involvement in organic transformations highlights a fascinating renaissance of this simplest alkyne molecule.

show abstract

A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application

et al. 2016

View full text Add to dashboard Cite

Four new titanium catecholate complexes – [Ti2(Cat)2(CatH)2(OCH3)2(CH3OH)2] (1; Cat = C6H4O22–), [Ti2(4tBuCat)4(CH3OH)2]·2CH3OH (2·2CH3OH; 4tBuCat = [4‐t‐C4H9‐C6H3O2]2–), [Ti(Cat)2(dmf)2] (3; dmf = N,N‐dimethylformamide), and [Na(dme)Ti(Cat)3]2[Na(dme)CH3OH]2 (4; dme = 1,2‐dimethoxyethane) – have been obtained by treatment of Ti(OCH3)4 with catechols in methanol and structurally characterized. Complex 3 is the first example of a neutral mononuclear titanium catecholate containing more than one catechol molecule per titanium atom. Complexes 1 and 2 are neutral dimers in the solid state, each with a catechol/Ti ratio equal to 2 and featuring one of the catechol ligands bridging two titanium centres in a singly bridging chelate µ2‐(O,O′,O′) mode. The other catechol molecule is either a terminal bidentate chelating ligand (complex 2) or a Ti monodentate ligand (complex 1). Complex 4 is a heterometallic aryloxide complex with a tetrameric [{Na(dme)Ti(Cat)3)2]2– (Ti2Na2) core as an anionic moiety and Na ions, solvated by methanol and dme ligands – [{Na(dme)(CH3OH)}2]2+ – as a cationic counterpart. Each Ti centre in 4 is octahedrally coordinated by three catechol ligands, demonstrating three distinct types of bridging modality. It was shown that 1–4 effectively catalyze the selective homogeneous hydrogenation of acetylene to ethylene. Various kinetic relationships were determined and analyzed, enabling a reaction pathway for this catalytic reaction to be proposed.

show abstract

Inorganic clusters with a [Fe₂MoOS₃] core—a functional model for acetylene reduction by nitrogenases

Cited by 4 publications

References 51 publications

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

Acetylene in Organic Synthesis: Recent Progress and New Uses

A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application

Contact Info

Product

Resources

About

Inorganic clusters with a [Fe2MoOS3] core—a functional model for acetylene reduction by nitrogenases

Cited by 4 publications

References 51 publications

Metal–Sulfur Compounds in N2 Reduction and Nitrogenase-Related Chemistry

Metal–Sulfur Compounds in N2 Reduction and Nitrogenase-Related Chemistry

Acetylene in Organic Synthesis: Recent Progress and New Uses

A Family of Titanium Complexes with Catechol Ligands: Structural Investigation and Catalytic Application

Contact Info

Product

Resources

About

Inorganic clusters with a [Fe₂MoOS₃] core—a functional model for acetylene reduction by nitrogenases

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry