Synthesis of Bimetallic Cubane-Type Mo2M2S4 Clusters (M = Ir, Rh, Ru) and Reductive Cleavage of the N−N Bond of 1,1-Methylphenylhydrazine Affording N-Methylaniline Using Mo2Ir2S4 and Mo2Rh2S4 Clusters as Catalyst Precursors

Seino, Hidetake; Masumori, Tadao; Hidai, Masanobu; Mizobe, Yasushi

doi:10.1021/om030231p

Cited by 36 publications

(11 citation statements)

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“…Catalytic reduction of an organohydrazine (MePhNNH 2 ) was attained by [Cp* 2 M 2 S 4 {Mo(O)Cl 2 }{MoCl 2 (DMF)}] (M = Ir ( 67 ), Rh ( 68 )), and these were prepared from the reactions of [(Cp*MCl) 2 (μ-SH) 2 ] (M = Ir, Rh) with [{(DMF) 3 (O)Mo} 2 (μ-S) 2 ] 2+ and [NMe 4 ][Cl] (Scheme a) . In the presence of 10 mol % of 67 or 68 , Cp 2 Co (2 equiv), and [LutH][Cl] (2 equiv), MePhNNH 2 was converted into MePhNH (and NH 3 ), and the yield of MePhNH was quantified as 64% (by 67 ) and 31% (by 68 ), respectively (Scheme b).…”

Section: Metal–sulfur Clusters In Nitrogenase-related Chemistrymentioning

confidence: 99%

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

2020

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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.

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Section: Metal–sulfur Clusters In Nitrogenase-related Chemistrymentioning

confidence: 99%

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

2020

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“…Our recent research has focused on syntheses of transition-metal sulfido clusters and exploration of their reactivities to activate small molecules effectively. – For the systems using metal sulfido clusters, it may be expected that reaction proceeds with retention of their multimetallic core structures even under relatively forcing conditions, owing to the presence of firmly bonded sulfido bridges. In this paper, we wish to describe the structures and reactivities of a series of new Ir sulfido clusters having hydrido ligands, which have been synthesized from the reactions of the Ir hydrido complex [(Cp*Ir) 2 (μ-H) 3 ][BF 4 ] ( 1 ; Cp* = η 5 -C 5 Me 5 ) with controlled amount of the sulfido source.…”

Section: Introductionmentioning

confidence: 99%

Properties and Reactivities of the Hydrido Ligands in Iridium Sulfido Clusters Relevant to Activation and Production of H₂

et al. 2008

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Sulfido-hydrido clusters whose cores consist of three to six iridium atoms, [(Cp*Ir) 3 (µ 3 -S)(µ 2 -H) 3 ][BF 4 ] (2), [(Cp*Ir) 4 (µ 3 -S) 2 (µ 2 -H) 3 ][BF 4 ] (3), [(Cp*IrH) 2 (Cp*Ir)(µ 3 -S)(µ 2 -H) 2 ], [(Cp*IrH) 4 (µ 4 -S)(µ 2 -H) 2 ], and [(Cp*Ir) 5 Ir(µ 3 -S) 5 H], were isolated from the reactions of [(Cp*Ir) 2 (µ 2 -H) 3 ][BF 4 ] (Cp* ) η 5 -C 5 Me 5 ) with NaSH in MeOH. Treatment of 2 with KOBu t afforded the deprotonated product [(Cp*Ir) 3 (µ 3 -S)(µ-H) 2 ] (7), which was protonated by HBF 4 to give 2 reversibly. Addition of HBF 4 to 3 formed the dicationic cluster [(Cp*Ir) 4 (µ 3 -S) 2 (µ-H) 2 ][BF 4 ] 2 (10) with concurrent evolution of H 2 , which was converted back to 3 under H 2 atmosphere in the presence of excess pyridine at 50 °C. In contrast, reactions of 10 with H 2 conducted in the presence of various alkylamines at 20-50 °C afforded the mixtures of 3 and its stereoisomer 11. Conversion of 10 into 3 was also achieved by the reaction with 2 equiv of Cp 2 Co in the presence of [Et 3 NH][BF 4 ], which furnished the cycle of reducing H + into H 2 mediated by the Ir 4 S 2 cluster. Cluster 10 readily reacted with CO (1 atm) at 20 °C to give [(Cp*Ir) 4 (µ 3 -S) 2 (µ-H) 2 (CO)][BF 4 ] 2 ( 13), where the CO ligand was bound in an end-on fashion to one of the two Ir centers connected to two µ 3 -sulfido ligands. Analogous adduct formation was observed in the reaction of 10 with 1 equiv of XyNC (Xy ) 2,6-dimethylphenyl), yielding two stereoisomers of [(Cp*Ir) 4 (µ 3 -S) 2 (µ-H) 2 (CNXy)][BF 4 ] 2 , one of which was the analogue of 13 and the other had the XyNC ligand coordinating to the same Ir site but with the inverted orientation around the metal. On the other hand, treatment of 10 with excess N 2 H 4 gave the hydrazine cluster [(Cp*Ir) 4 (µ 3 -S) 2 (µ 2 -H) 2 (N 2 H 4 ) 2 ][BF 4 ] 2 , in which two terminal hydrazine ligands were bonded to one of two Ir sites supported by only one µ 3 -sulfido ligand. On the basis of these findings about the adduct formations, reaction pathways of 10 with H 2 in the presence of bases are discussed. Structures of all new clusters reported here were determined by spectroscopic methods and, except for 7, by X-ray crystallography.

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“…[1][2][3][4] In particular, several pseudo-octahedral Rh-Cp* (Cp* = C 5 Me 5 ) complexes produced molecular species, dimers, or polygons when treated with tailored ligands, depending on the nature of the used ligands. [5][6][7][8][9][10][11][12][13][14][15] For instance, Yamamoto and co-workers reported on the formation molecular species from the reactions of isocyanoazobenzene with Rh-Cp*. 11 Jin's group prepared tetranuclear rectangular Rh-Cp* complexes by employing bis(pyridine)-or dicarboxylate-type linking ligands.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of RhCp* Complexes Containing Labile Ligands toward Potential Linking Ligands Containing Terminal Thiophene or Furan Rings:Preparation and Structures of [Cp^Rh(L¹)Cl₂], [Cp^Rh(η²-NO₃)(L¹)](OTf),and {[Rh(L²)] · (OTf)}_∞[L¹= 1,2-Bis((thiophen-2-yl)methylene)hydrazine); L²= 1,2-Bis((furan-2-yl)methylene)hydrazine]

Lee¹,

Lee²

2010

Bulletin of the Korean Chemical Society

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Synthesis of Bimetallic Cubane-Type Mo₂M₂S₄ Clusters (M = Ir, Rh, Ru) and Reductive Cleavage of the N−N Bond of 1,1-Methylphenylhydrazine Affording N-Methylaniline Using Mo₂Ir₂S₄ and Mo₂Rh₂S₄ Clusters as Catalyst Precursors

Cited by 36 publications

References 59 publications

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

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

Properties and Reactivities of the Hydrido Ligands in Iridium Sulfido Clusters Relevant to Activation and Production of H₂

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Synthesis of Bimetallic Cubane-Type Mo2M2S4 Clusters (M = Ir, Rh, Ru) and Reductive Cleavage of the N−N Bond of 1,1-Methylphenylhydrazine Affording N-Methylaniline Using Mo2Ir2S4 and Mo2Rh2S4 Clusters as Catalyst Precursors

Cited by 36 publications

References 59 publications

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

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

Properties and Reactivities of the Hydrido Ligands in Iridium Sulfido Clusters Relevant to Activation and Production of H2

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Resources

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Synthesis of Bimetallic Cubane-Type Mo₂M₂S₄ Clusters (M = Ir, Rh, Ru) and Reductive Cleavage of the N−N Bond of 1,1-Methylphenylhydrazine Affording N-Methylaniline Using Mo₂Ir₂S₄ and Mo₂Rh₂S₄ Clusters as Catalyst Precursors

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

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

Properties and Reactivities of the Hydrido Ligands in Iridium Sulfido Clusters Relevant to Activation and Production of H₂