A5060292429- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Metalloenzymes and iron-sulfur proteins
- Crystallography and molecular interactions
- Organometallic Complex Synthesis and Catalysis
- Electrocatalysts for Energy Conversion
- Inorganic Chemistry and Materials
- Ammonia Synthesis and Nitrogen Reduction
- Metal complexes synthesis and properties
- Asymmetric Hydrogenation and Catalysis
- Catalytic Cross-Coupling Reactions
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Carbon dioxide utilization in catalysis
- Hydrogen Storage and Materials
- Organoboron and organosilicon chemistry
- Synthesis and characterization of novel inorganic/organometallic compounds
- Metal-Catalyzed Oxygenation Mechanisms
- Magnetism in coordination complexes
- Coordination Chemistry and Organometallics
- Catalytic C–H Functionalization Methods
- Synthetic Organic Chemistry Methods
- Cyclopropane Reaction Mechanisms
- Ferrocene Chemistry and Applications
- Polyoxometalates: Synthesis and Applications
- Metal-Organic Frameworks: Synthesis and Applications
Kyoto University
2009-2025
Kyoto University Institute for Chemical Research
2021-2025
Kyoto Bunkyo University
2022-2023
Instituto de Investigaciones Químicas
2022
Nagoya University
2011-2020
Tokyo Institute of Technology
2000-2020
Graduate School USA
2020
Japan Science and Technology Agency
2015-2017
University of Münster
2008-2012
Technische Universität Berlin
2012
Merging cooperative Si-H bond activation and electrophilic aromatic substitution paves the way for C-3-selective indole C-H functionalization under electronic not conventional steric control. The is heterolytically split by Ru-S of a coordinatively unsaturated cationic ruthenium(II) complex, forming sulfur-stabilized silicon electrophile. Wheland intermediate subsequent Friedel-Crafts-type process assumed to be deprotonated sulfur atom, no added base required. overall catalysis proceeds...
Half-sandwich iron complexes of N-heterocyclic carbenes, Cp*Fe(L(R))Cl (2a; L(Mes) = 1,3-dimesityl-imidazol-2-ylidene, 2b; L(iPr) 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, Cp* eta(5)-C5Me5), have been synthesized by the reaction Cp*Fe{N(SiMe3)2} (1) with corresponding imidazolium salts. Treatment 2a either methyllithium or phenyllithium replaces chloride a methyl phenyl group, generating Cp*Fe(L(Mes))R (3a; R Me, 3b; Ph). These complexes, in turn, undergo cyclometalation at elevated...
The B-H bond of typical boranes is heterolytically split by the polar Ru-S a tethered ruthenium(II) thiolate complex, affording hydride and borenium ions with dative interaction sulfur atom. These stable adducts were spectroscopically characterized, in one case, activation step was crystallographically verified, snapshot σ-bond metathesis. derived from 9-borabicyclo[3.3.1]nonane dimer [(9-BBN)2], pinacolborane (pinBH), catecholborane (catBH) allowed for electrophilic aromatic substitution...
A coordinatively unsaturated iron-methyl complex having an N-heterocyclic carbene ligand, [Cp*Fe(L(Me))Me] (1; Cp*=eta(5)-C(5)Me(5), L(Me)=1,3,4,5-tetramethyl-imidazol-2-ylidene), is synthesized from the reaction of [Cp*Fe(TMEDA)Cl] (TMEDA=N,N,N',N'-tetramethylethylenediamine) with methyllithium and L(Me). Complex 1 found to activate C-H bonds furan, thiophene, benzene, giving rise aryl complexes, [Cp*Fe(L(Me))(aryl)] (aryl=2-furyl (2), 2-thienyl (3), phenyl (4)). The bond cleavage reactions...
Multiple iron atoms bridged by hydrides is a common structural feature of the active species that have been postulated in biological and industrial reduction N2. In this study, reactions an Fe(II) amide complex with pinacolborane presence/absence phosphines afforded series hydride-supported [Fe4] [Fe6] clusters Fe4(μ-H)4(μ3-H)2{N(SiMe3)2}2(PR3)4 (PR3 = PMe3 (2a), PMe2Ph (2b), PEt3 (2c)), Fe6(μ-H)10(μ3-H)2(PMe3)10 (3), (η6-C7H8)Fe4(μ-H)2{μ-N(SiMe3)2}2{N(SiMe3)2}2 (4), which were characterized...
[NiFe] hydrogenase, the enzyme of which catalyzes reversible oxidation molecular hydrogen to protons and electrons, contains a unique heterodinuclear thiolate-bridged Ni-Fe complex in iron center is coordinated by CO CN. We have synthesized dithiolate-bridged complexes bearing CN ligands model active hydrogenase. The containing [(CN)2(CO)2Fe(mu-S2)NiS2] framework are closest yet structural models
A coordinatively unsaturated dinuclear iron(II) complex of bulky thiolates, [(TipS)Fe(micro-SDmp)]2 (1; Tip = 2,4,6-(i)Pr(3)C(6)H(2), Dmp 2,6-(mesityl)(2)C(6)H(3)), was synthesized from stepwise reactions Fe{N(SiMe(3))2}2 with 1 equiv HSDmp and then HSTip. Complex found to react elemental sulfur (S8) in toluene generate a new class [8Fe-7S] cluster, [(DmpS)Fe(4)S(3)]2(micro-SDmp)2(micro-STip)(micro(6)-S) (2). The cluster 2 also produced one-pot + HSTip S8 (8:6:10:7/8)...
The zirconocene complex [{(C₆F₅)₂B-(CH₂)₃-Cp}(Cp-PtBu₂)ZrCl₂] (6; Cp=cyclo-C₅H₄) was prepared by hydroboration of [(allyl-Cp)(Cp-PtBu₂)ZrCl₂] (5) with HB(C₆F₅)₂ ("Piers' borane"). It represents a frustrated Lewis pair (FLP) in which both the acid and base were attached at metallocene framework. Its reaction 1-pentyne did not result 1,2-addition or deprotonation FLP, but rather 1,1-carboboration triple bond, thereby obtaining Z/E mixture (1.2:1) respective organometallic substituted alkenes...
N-heterocyclic carbene (NHC) adducts of iron dichloride, (IMes)2FeCl2 (1a; IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and (IEtPh*)2FeCl2 (1b; IEtPh* 1,3-bis((R)-1′-phenylethyl)imidazol-2-ylidene), were prepared in good yields from the reactions Fe{N(SiMe3)2}2 with imidazolium salts. While atom 1a has a tetrahedral geometry, replacement chlorides by methyl groups via treatment MeLi led to formation square-planar complex trans-(IMes)2FeMe2 (2). The molecular structures complexes...
The heterolytic splitting of hydrosilanes by ruthenium(<sc>ii</sc>) thiolates is illuminated a combined spectroscopic, crystallographic, and computational analysis.
Abstract The FeMo-cofactor of nitrogenase, a metal–sulfur cluster that contains eight transition metals, promotes the conversion dinitrogen into ammonia when stored in protein. Although various clusters have been synthesized over past decades, their use activation N 2 has remained challenging, and even extracted from nitrogenase is not able to reduce . Herein, we report by molybdenum titanium. An moiety bridging two [Mo 3 S 4 Ti] cubes converted NH H upon treatment with Brønsted acids...
The [8Fe−7S] core of the P-clusters in nitrogenases is unique among known [Fe−S] clusters which are essential to electron-transfer processes nature. cluster has been thought unstable and exist only protein environments. We found that this unusual structure can be self-assembled from reaction Fe(II) bis-amide, tetramethylthiourea, 2,4,6-triisopropylbenzenethiol, elemental sulfur a specific mole ratio. complex isolated therefrom closely resembles reduced form (PN) P-clusters, while...
Side-on matters: When dinitrogen bridges two Group 4 metal centers in the side-on binding mode, reactivity of N2 unit is enhanced, as evidenced by unprecedented reactions with H2, alkynes, silanes, isocyanates, and now carbon dioxide (see scheme). This Highlight summarizes a number recent breakthroughs functionalization bimetallic complexes, culminating reaction CO2 dihafium derivative. Activating molecular nitrogen soluble complexes longstanding challenge inorganic chemistry.1 simple,...
A series of [Tm(Me)M(mu-Cl)]2 and Tm(R)MCl (Tm(R) = tris(mercaptoimidazolyl)borate; R Me, tBu, Ph, 2,6-iPr2C6H3 (Ar); M Mn, Fe, Co, Ni) complexes have been prepared by treatment NaTm(Me) or LiTm(R) with an excess amount metal(II) chlorides, MCl2. Treatment (R Ar) NaI led to a halide exchange afford Tm(R)MI. The molecular structures (M Ni), [Tm(Me)Ni(mu-Br)]2, Tm(tBu)MCl Co), Tm(Ph)MCl Tm(Ar)MCl Tm(Ph)MI Tm(Ar)MI determined X-ray crystallography. Tm(R) ligands occupy the tripodal coordination...
Abstract Hydrogenases catalyze the reversible oxidation of H 2 , which is crucial for anaerobic metabolism microorganisms. They attract growing interest in connection with ‐based energy systems. [NiFe] hydrogenase most common type among currently known hydrogenases, and its active site consists an “organometallic” Fe–Ni complex supported by cysteinyl thiolate ligands. This review presents overview synthesis, properties, reactions thiolate‐bridged iron–nickel complexes that model hydrogenase.
Facile H2 heterolysis was found to be mediated by coordinatively unsaturated Cp*Ir and Cp*Rh thiolate complexes. The reaction of iridium complex is reversible, the formation an intermediary Ir-H/thiol detected. reversible conversion between complex+H2 hydride complex+thiol provides intriguing functional model [NiFe] hydrogenase.
A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with Ru–S bond is reported. The assumed to fulfill dual role activating the Si–H release silicon electrophile abstracting an α-proton from intermediate silylcarboxonium ion, only liberating dihydrogen as sole byproduct. Reaction rates are exceedingly high at room temperature very low loadings catalyst.
Abstract The Mo nitrogenase catalyzes the ambient reduction of N 2 to NH 3 at its M‐cluster site. A complex metallocofactor with a core composition [MoFe 7 S 9 C], M‐cluster, can be extracted from protein scaffold and used facilitate catalytic CN − , CO, CO into hydrocarbons in isolated state. Herein, we report synthesis, structure, reactivity an asymmetric analogue 5 ]. This analogue, referred as Mo‐cluster, is first synthetic example mimic Fe positioned opposite ends cluster. Moreover,...
Nanoclusters are nanometer-sized molecular compounds characterized by significant metal–metal bonding and low average oxidation states, they exhibit unique properties distinct from those of small metal complexes or nanoparticles. Unlike noble metals stable in metallic forms, the synthesis iron clusters has been precluded relatively weak iron–iron bonds high reactivity state iron, despite extensive history compounds. Here, we report characterization a cationic 55-atom cluster with 1.2 nm...
The synthesis and full characterization of 1,4-dilithio-1,4-bis(triisopropylsilyl)-2,3-diphenylbuta-1,3-diene (1b) are reported. This molecule featuring extremely bulky silyl groups at the 1- 4-positions serves as a precursor for of...