Efficient hydrogenation of biomass-derived cyclic di-esters to 1,2-diols

Efficient hydrogenation of biomass-derived cyclic di-esters to 1,2-diols:

Chem. Commun., 2011 DOI: 10.1039/C1CC15778G

Ekambaram Balaraman, Eran Fogler, David Milstein
Hydrogenation of cyclic diesters to diols has been accomplished for the first time.

Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds

Synthesis and Hydride
Transfer Reactions of Cobalt
and Nickel Hydride Complexes to BX3 Compounds:

Inorganic Chemistry

DOI: 10.1021/ic200857x

Dinucleating Naphthyridine-Based Ligand for Assembly of Bridged Dicopper(I) Centers: Three-Center Two-Electron Bonding Involving an Acetonitrile Donor

Dinucleating Naphthyridine-Based Ligand for Assembly of Bridged Dicopper(I) Centers: Three-Center Two-Electron Bonding Involving an Acetonitrile Donor:

Unusual bonding: A ligand system that promotes formation of a rare μ-η¹:η¹ acetonitrile-bridged dicopper(I) complex (see picture) has been developed. The acetonitrile ligand is involved in a three-center two-electron bond supported by a cuprophilic interaction. The labile acetonitrile ligand can be substituted with xylyl isocyanide or CO.

From Letko's present work-group. Highly relevant to his thesis work.

Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase

Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase:

Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase

Nature Chemistry.
doi:10.1038/nchem.1180

James M. Camara & Thomas B. Rauchfuss

The fastest catalysts in nature for producing and oxidizing hydrogen are [FeFe]-hydrogenases, which make use of an extra one-electron redox equivalent from an iron-sulfur cluster that is outside the core. Now, a ferrocene-based ligand that oxidizes at mild potential performs this cluster's role in an excellent synthetic hydrogenase model.

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO2)3][PF6]

Late-Metal Nitrosyl Cations:
Synthesis and Reactivity
of [Ni(NO)(MeNO2)3][PF6]:

Inorganic Chemistry

DOI: 10.1021/ic201821t

Flash and Continuous Photolysis Kinetic Studies of the Iron–Iron Hydrogenase Model (μ-pdt)[Fe(CO)3]2 in Different Solvents

Flash and Continuous Photolysis
Kinetic Studies of
the Iron–Iron Hydrogenase Model (μ-pdt)[Fe(CO)3]2 in Different Solvents:

Inorganic Chemistry

DOI: 10.1021/ic201523r

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4:

Dalton Trans., 2012, Advance Article DOI: 10.1039/C1DT11428J, Paper

Robert J. Wright, Wei Zhang, Xinzheng Yang, Meg Fasulo, T. Don Tilley
Proposed proton reduction intermediates were synthesized and studied computationally, which suggests protonation first at iron and then thiolate. This species then undergoes an intramolecular acid-base reaction to form hydrogen.

Directing the Reactivity of [HFe4N(CO)12]− toward H+ or CO2 Reduction by Understanding the Electrocatalytic Mechanism

Directing the Reactivity of [HFe4N(CO)12]− toward H+ or CO2 Reduction by Understanding the Electrocatalytic Mechanism:

Journal of the American Chemical Society

DOI: 10.1021/ja208312t

Proton-Coupled Electron Shuttling in a Covalently Linked Ruthenium–Copper Heterodinuclear Complex

Proton-Coupled Electron Shuttling in a Covalently Linked Ruthenium–Copper Heterodinuclear Complex:

Journal of the American Chemical Society

DOI: 10.1021/ja208141b

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4

Isolation, observation, and computational modeling of proposed intermediates in catalytic proton reductions with the hydrogenase mimic Fe2(CO)6S2C6H4:

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C1DT11428J, Paper

Robert J. Wright, Wei Zhang, Xinzheng Yang, Meg Fasulo, T. Don Tilley
Proposed proton reduction intermediates were synthesized and studied computationally, which suggests protonation first at iron and then thiolate. This species then undergoes an intramolecular acid-base reaction to form hydrogen.
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Ring-Slippage and Multielectron Redox Properties of Fe/Ru/Os–Bis(arene) Complexes: Does Hapticity Change Really Cause Potential Inversion?

Ring-Slippage and Multielectron Redox Properties of Fe/Ru/Os–Bis(arene) Complexes: Does Hapticity Change Really Cause Potential Inversion?:

Journal of the American Chemical Society

DOI: 10.1021/ja205169c

Cascade Catalysis for the Homogeneous Hydrogenation of CO2 to Methanol

Cascade Catalysis for the Homogeneous Hydrogenation of CO2 to Methanol:

Journal of the American Chemical Society

DOI: 10.1021/ja208760j

Mechanistic and Physiological Implications of the Interplay among Iron–Sulfur Clusters in [FeFe]-Hydrogenases. A QM/MM Perspective

Mechanistic and Physiological Implications of the Interplay among Iron–Sulfur Clusters in [FeFe]-Hydrogenases. A QM/MM Perspective:

Journal of the American Chemical Society

DOI: 10.1021/ja205542k

Photocatalytic Splitting of CS2 to S8 and a Carbon–Sulfur Polymer Catalyzed by a Bimetallic Ruthenium(II) Compound with a Tertiary Amine Binding Site: Toward Photocatalytic Splitting of CO2?

Photocatalytic Splitting of CS2 to S8 and a Carbon–Sulfur Polymer Catalyzed by a Bimetallic Ruthenium(II) Compound with a Tertiary Amine Binding Site: Toward Photocatalytic Splitting of CO2?:

Inorganic Chemistry

DOI: 10.1021/ic2008045

Highly Efficient Oxidation of Water by a Molecular Catalyst Immobilized on Carbon Nanotubes

Highly Efficient Oxidation of Water by a Molecular Catalyst Immobilized on Carbon Nanotubes:

A successful team: A molecular device based on multiwalled carbon nanotubes functionalized by a mononuclear ruthenium catalyst has been shown to split water electrochemically (see picture; ITO=indium tin oxide). The readily prepared electrode showed excellent electrocatalytic activity for the oxidation of water, a high current density, and a low overpotential, and constitutes one step forward in the design of artificial photosynthetic systems.

Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations

Comprehensive Thermodynamics
of Nickel Hydride Bis(Diphosphine)
Complexes: A Predictive Model through Computations:

Organometallics

DOI: 10.1021/om200645x

N-Sulfinylcarboximidates as a New Class of Chiral Bidentate Ligands: Application to Asymmetric Coordination Chemistry

N-Sulfinylcarboximidates as a New Class of Chiral Bidentate Ligands: Application to Asymmetric Coordination Chemistry:

A class of its own: A new chiral bidentate ligand, N-acetyl-tert-butanesulfinamide, was applied to the asymmetric synthesis of octahedral ruthenium polypyridyl complexes. This new class of ligands coordinates in a bidentate fashion through its deprotonated N-sulfinylcarboximidate form (see scheme). This sulfinamide auxiliary should be highly valuable for the efficient asymmetric synthesis of a large variety of ruthenium complexes.

Assessment of the Electronic Properties of P ligands Stemming from Secondary Phosphine Oxides

Assessment of the Electronic Properties of P ligands Stemming from Secondary Phosphine Oxides:

Abstract

We report the study of the net donating ability of monodentate and bidentate P ligands stemming from secondary phosphine oxides (SPOs). We experimentally measured and/or calculated the frequencies of CO stretching modes of various metal carbonyl complexes. The inferred electronic properties of the ligands span an unprecedented range, going from π-accepting phosphite-like compounds, to extremely electron-donating ligands outclassing N-heterocyclic carbenes.

A generous donation: The net donating ability of monodentate and bidentate P ligands stemming from secondary phosphine oxides (SPOs) is spread on an unprecedented range: from π-accepting phosphite-like compounds, as far as extremely electron-donating ligands outclassing N-heterocyclic carbenes (NHCs; see figure).

Rapid Water Reduction to H2 Catalyzed by a Cobalt Bis(iminopyridine) Complex

Rapid Water Reduction to H2 Catalyzed by a Cobalt Bis(iminopyridine) Complex:

Journal of the American Chemical Society

DOI: 10.1021/ja2078015

Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride:

Chem. Commun., 2011, Advance ArticleDOI: 10.1039/C1CC14856G, Communication

Kamalraj V. Rajendran, Declan G. Gilheany
We describe a method to replace O or S with BH₃, achirally or stereospecifically, under mild conditions.

dppeO2 deprotonation, dehydogenation to dppvO2 to dppv(BH3)2

The Production of 5-Hydroxymethylfurfural from Fructose in Isopropyl Alcohol: A Green and Efficient System

The Production of 5-Hydroxymethylfurfural from Fructose in Isopropyl Alcohol: A Green and Efficient System:

Solving problems: An isopropyl alcohol-mediated reaction system for the production of 5-hydroxymethylfurfural (HMF) from fructose reaches a yield of up to 87 %. The solvent can be easily recycled by evaporation, giving the HMF product. The system avoids the use of large amounts of organic solvent, has a minimal environmental impact, and offers a new route to large-scale economically viable processes.

Computational Evidence for Hydrogen Generation by Reductive Cleavage of Water and α-H Abstraction on a Molybdenum Complex

Computational Evidence for Hydrogen Generation by Reductive Cleavage of Water and α-H Abstraction on a Molybdenum Complex:

Long-standing hypothesis now verified: H₂ generation by reductive cleavage of water and α-H abstraction has long been considered as a possible mechanism for reduction of water to H₂, but a clear example was not established up to now. Detailed DFT calculations now reveal that this process is energetically favorable on an Mo^I site (see picture). Formation of H₂ by this mechanism is also feasible, albeit less favorable, on an Mo^II site.

Biosynthesis of Isoprene Units: Mössbauer Spectroscopy of Substrate and Inhibitor Binding to the [4Fe-4S] Cluster of the LytB/IspH Enzyme

Biosynthesis of Isoprene Units: Mössbauer Spectroscopy of Substrate and Inhibitor Binding to the [4Fe-4S] Cluster of the LytB/IspH Enzyme:

A fascinating cube: LytB, an enzyme containing a [4Fe-4S] cluster, catalyzes the last step of the methylerythritol phosphate pathway, a target for antibacterial and antiparasitic drugs. Field-dependent Mössbauer spectroscopy showed that the unique fourth iron atom of the [4Fe-4S] cluster coordinates to the hydroxy group of the substrate (see picture) and to the amino and thiol moieties of two potent inhibitor substrate analogues.

Synthesis, Isolation and Structural Characterisation of Alkoxytitanium Triflate Complexes

Synthesis, Isolation and Structural Characterisation of Alkoxytitanium Triflate Complexes:

Abstract

Treatment of [Ti(OiPr)₄] with trimethylsilyl triflate results in the formation of [Ti(OiPr)₃(OTf)] (2) in high yield. Subsequent treatment of the triflate derivative 2 with a series of facially coordinating N₃-donor ligands results in the production of a series of charge-separated metal alkoxide salts of the general formula [{L}Ti(OiPr)₃][OTf] {L = tris(pyrazolyl)methane (3a), 1,3,5-triethyl-1,3,5-triazacyclohexane (3b), 1,3,5-tribenzyl-1,3,5-triazacyclohexane (3c), 1,3,5-tris(p-fluorobenzyl)-1,3,5-triazacyclohexane (3d), and 1,3,5-tris[(1S)-1-phenylethyl]-1,3,5-triazacyclohexane (3e)}. The products were characterized by ¹H and ¹³C NMR spectroscopy and in the case of 3a–c by single-crystal X-ray diffraction. Reaction of 2 with 1,3,5-triphenyl-1,3,5-triazacyclohexane results in the formation of complex 4 [{L′}₂Ti(OiPr)₂(OTf)₂], which contains two 3,4-dihydroquinazoline ligands (L′), a result of catalytic activation of the triazacyclohexane ligands by [Ti(OiPr)₃(OTf)] towards electrophilic aromatic substitution.

New alkoxytitanium triflate complexes containing a range of facially coordinating N₃ ligands were prepared and structurally characterised. Reaction of [Ti(OiPr₃)OTf] with 1,3,5-triphenyl-1,3,5-triazacyclohexane results in the catalytic activation of the triazacyclohexane ligands and isolation of a new titanium complex [{L′}₂Ti(OiPr)₂(OTf)₂] (L′ = 3-phenyl-3,4-dihydroquinazoline).

Interesting part: Reaction of 1,3,5-triphenyl-1,3,5-triazacyclohexane with [Ti(OiPr)₃(OTf)] yields a complex where the ligands are 3,4-dihydroquinazoline (See the figure)

Carbonylation of Nitrobenzene in Methanol with Palladium Bidentate Phosphane Complexes: An Unexpectedly Complex Network of Catalytic Reactions, Centred around a Pd–imido Intermediate

Carbonylation of Nitrobenzene in Methanol with Palladium Bidentate Phosphane Complexes: An Unexpectedly Complex Network of Catalytic Reactions, Centred around a Pd–imido Intermediate:

Abstract

The reactivity of palladium complexes of bidentate diaryl phosphane ligands (P₂) was studied in the reaction of nitrobenzene with CO in methanol. Careful analysis of the reaction mixtures revealed that, besides the frequently reported reduction products of nitrobenzene [methyl phenyl carbamate (MPC), N,N′-diphenylurea (DPU), aniline, azobenzene (Azo) and azoxybenzene (Azoxy)], large quantities of oxidation products of methanol were co-produced (dimethyl carbonate (DMC), dimethyl oxalate (DMO), methyl formate (MF), H₂O, and CO). From these observations, it is concluded that several catalytic processes operate simultaneously, and are coupled via common catalytic intermediates. Starting from a P₂Pd⁰ compound formed in situ, oxidation to a palladium imido compound P₂Pd^IINPh, can be achieved by de-oxygenation of nitrobenzene 1) with two molecules of CO, 2) with two molecules of CO and the acidic protons of two methanol molecules, or 3) with all four hydrogen atoms of one methanol molecule. Reduction of P₂Pd^IINPh to P₂Pd⁰ makes the overall process catalytic, while at the same time forming Azo(xy), MPC, DPU and aniline. It is proposed that the Pd–imido species is the central key intermediate that can link together all reduction products of nitrobenzene and all oxidation products of methanol in one unified mechanistic scheme. The relative occurrence of the various catalytic processes is shown to be dependent on the characteristics of the catalysts, as imposed by the ligand structure.

Pd-catalyzed carbonylation of PhNO₂ with CO in CH₃OH has been studied. PhNO₂ is reduced by CO and, surprisingly, also by CH₃OH as (co-)reductant, leading to a proposed PdNPh complex. This Pd–imido compound is thought to be the key intermediate in a complex network of catalytic reactions, linking together the formation of all observed CH₃OH oxidation products and PhNO₂ reduction products (see scheme).

Tiddo was a Bachelor, Master and present PhD student (with multiple skills) works for my former work group. This project is for Shell to make MDI in greener ways. This is not relevant to our work, you may read only if you are interested. His work on anion-pi interactions are very famous in that field.

http://onlinelibrary.wiley.com/doi/10.1002/anie.201100208/pdf