Bifunctional Tungstate Catalyst for Chemical Fixation of CO2 at Atmospheric Pressure

Bifunctional Tungstate Catalyst for Chemical Fixation of CO2 at Atmospheric Pressure:

No pressure: A simple monomeric tungstate, [WO₄]²⁻, serves as a highly efficient homogeneous catalyst for various transformations of CO₂ at atmospheric pressure. The tungsten-oxo moiety activates CO₂ and the substrate simultaneously. The catalyst system is high yielding and applicable to a wide range of substrates such as amines (see scheme), 2-aminobenzonitriles, and propargylic alcohols.

Interesting use of diaminobenzene as CO acceptor and H2 donor.

Formation and Characterization of Gaseous Adducts of Carbon Dioxide to Magnesium, (CO2)MgX− (X=OH, Cl, Br)

Formation and Characterization of Gaseous Adducts of Carbon Dioxide to Magnesium, (CO2)MgX− (X=OH, Cl, Br):

A good fix: The structure and chemical reactivity of a reduced form of CO₂ bonded to magnesium, XMg(η²-O₂C)⁻, is reported. Upon reaction with water it loses CO, while it adds CH₃ upon reaction with alkyl halides, thereby signifying nucleophilicity of the carbon atom in XMg(η²-O₂C)⁻ in S_N2 reactions.

Hydrogenation of Carbon Dioxide to Methanol by Using a Homogeneous Ruthenium–Phosphine Catalyst

Hydrogenation of Carbon Dioxide to Methanol by Using a Homogeneous Ruthenium–Phosphine Catalyst:

Simply efficient: The homogenously catalyzed hydrogenation of CO₂ to methanol is achieved by using a ruthenium phosphine complex under relatively mild conditions (see scheme; HNTf₂=bis(trifluoromethane)sulfonimide). This is the first example of CO₂ hydrogenation to methanol by using a single molecularly defined catalyst.

Chemoselective Transfer Hydrogenation to Nitroarenes Mediated by Cubane-Type Mo3S4 Cluster Catalysts

Chemoselective Transfer Hydrogenation to Nitroarenes Mediated by Cubane-Type Mo3S4 Cluster Catalysts:

Chemoselective cubes: Cubane-type [Mo₃S₄X₃(dmpe)₃]⁺ clusters (dmpe=1,2-(bis)dimethylphosphinoethane), in combination with an azeotropic 5:2 mixture of HCOOH and NEt₃ as the reducing agent, act as selective cluster catalysts (X=H) or precatalysts (X=Cl) for the transfer hydrogenation of functionalized nitroarenes, without the formation of hazardous hydroxylamines.

Studies of Inhibitor Binding to the [4Fe-4S] Cluster of Quinolinate Synthase

Studies of Inhibitor Binding to the [4Fe-4S] Cluster of Quinolinate Synthase:

Stop for NadA! A [4Fe-4S] enzyme, NadA, catalyzes the formation of quinolinic acid in de novo nicotinamide adenine dinucleotide (NAD) biosynthesis. A structural analogue of an intermediate, 4,5-dithiohydroxyphthalic acid (DTHPA), has an in vivo NAD biosynthesis inhibiting activity in E. coli. The inhibitory effect can be explained by the coordination of DTHPA thiolate groups to a unique Fe site of the NadA [4Fe-4S] cluster.

Mechanistic Insight fromActivation Parameters forthe Reaction of a Ruthenium Hydride Complex with CO2 inConventional Solventsand an Ionic Liquid

Mechanistic Insight from
Activation Parameters for
the Reaction of a Ruthenium Hydride Complex with CO2 in
Conventional Solvents
and an Ionic Liquid:

Inorganic Chemistry

DOI: 10.1021/ic300718v

Formation of N2O from a Nickel Nitrosyl:Isolation of the cis-[N2O2]2– Intermediate

Formation of N2O from a Nickel Nitrosyl:
Isolation of the cis-[N2O2]2– Intermediate:

Journal of the American Chemical Society

DOI: 10.1021/ja304204q

New Types of CO-ReleasingMolecules (CO-RMs), Basedon Iron Dithiocarbamate Complexes and [Fe(CO)3I(S2COEt)]

New Types of CO-Releasing
Molecules (CO-RMs), Based
on Iron Dithiocarbamate Complexes and [Fe(CO)3I(S2COEt)]:

Organometallics

DOI: 10.1021/om3003637

Stoichiometric CO2 reductions using a bis-borane-based frustrated Lewis pair

Stoichiometric CO2 reductions using a bis-borane-based frustrated Lewis pair:

Chem. Commun., 2012, Advance Article
DOI: 10.1039/C2CC33301E, Communication

Michael J. Sgro, Johannes Domer, Douglas W. Stephan
The bis-borane 1,2-C₆H₄(BCl₂)₂ forms an adduct with PtBu₃, but is still capable of exhibiting FLP reactivity with THF and CO₂.
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Iron(I) in Negishi Cross-CouplingReactions

Iron(I) in Negishi Cross-Coupling
Reactions:

Journal of the American Chemical Society

DOI: 10.1021/ja303250t

Time Resolved InfraredSpectroscopy: Kinetic Studiesof Weakly Binding Ligands in an Iron–Iron Hydrogenase ModelCompound

Time Resolved Infrared
Spectroscopy: Kinetic Studies
of Weakly Binding Ligands in an Iron–Iron Hydrogenase Model
Compound:

Inorganic Chemistry

DOI: 10.1021/ic300785z

Synthesis of Bis(N-heterocycliccarbene) Complexesof Iron(II) and Their Application in Hydrosilylation and TransferHydrogenation

Synthesis of Bis(N-heterocyclic
carbene) Complexes
of Iron(II) and Their Application in Hydrosilylation and Transfer
Hydrogenation:

Organometallics

DOI: 10.1021/om300298q

Formation and Characterization of Gaseous Adducts of Carbon Dioxide to Magnesium, (CO2)MgX− (X=OH, Cl, Br)

Formation and Characterization of Gaseous Adducts of Carbon Dioxide to Magnesium, (CO2)MgX− (X=OH, Cl, Br):

A good fix: The structure and chemical reactivity of a reduced form of CO₂ bonded to magnesium, XMg(η²-O₂C)⁻, is reported. Upon reaction with water it loses CO, while it adds CH₃ upon reaction with alkyl halides, thereby signifying nucleophilicity of the carbon atom in XMg(η²-O₂C)⁻ in S_N2 reactions.

Investigating the Roleof the Outer-Coordination Spherein [Ni(PPh2NPh-R2)2]2+ Hydrogenase Mimics

Investigating the Role
of the Outer-Coordination Sphere
in [Ni(PPh2NPh-R2)2]2+ Hydrogenase Mimics:

Inorganic Chemistry

DOI: 10.1021/ic300149x

Mechanistic Investigation of Improved Syntheses of Iridium(III)-Based OLED Phosphors

Mechanistic Investigation
of Improved Syntheses of
Iridium(III)-Based OLED Phosphors:

Organometallics

DOI: 10.1021/om300325y

useful Ir(III) reagent IrCl3(PR3(SR2)2

General and Selective Copper-Catalyzed Reduction of Tertiary and Secondary Phosphine Oxides: Convenient Synthesis of Phosphines

General and Selective
Copper-Catalyzed Reduction of
Tertiary and Secondary Phosphine Oxides: Convenient Synthesis of Phosphines:

Journal of the American Chemical Society DOI: 10.1021/ja301764m

It's tricky converting phosphine oxides to phosphines, silanes are the std reagents.

Donor–AcceptorProperties of Bidentate Phosphines.DFT Study of Nickel Carbonyls and Molecular Dihydrogen Complexes

Donor–Acceptor
Properties of Bidentate Phosphines.
DFT Study of Nickel Carbonyls and Molecular Dihydrogen Complexes:

Organometallics

DOI: 10.1021/om200456j

The reactions of pyridinyl thioesters with triirondodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations

The reactions of pyridinyl thioesters with triirondodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations:

Dalton Trans., 2012, Accepted Manuscript
DOI: 10.1039/C2DT30798G, Paper

Xiaoming Liu, Giuseppe Zampella
Reaction of Fe3(CO)12 with pyridinyl thioester liagnd PyCH2SCOCH3 (L1, Py = pyridin-2-yl) produced complex, [Fe2([small kappa]-COCH3)([small mu ]-SCH2Py)(CO)5] (1) (PyCH2S = pyridin-2-ylmethanethiolate). When complex 1 reacted with PPh3, a monosubstituted complex, [Fe2([small kappa]-COCH3)([small mu ]-SCH2Py)(CO)4PPh3] (2),...
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Hydrogen Evolution fromAliphatic Alcohols and 1,4-Selective Hydrogenation of NAD+ Catalyzed by a [C,N] and a [C,C] Cyclometalated Organoiridium Complexat Room Temperature in Water

Hydrogen Evolution from
Aliphatic Alcohols and 1,4-Selective Hydrogenation of NAD+ Catalyzed by a [C,N] and a [C,C] Cyclometalated Organoiridium Complex
at Room Temperature in Water:

Journal of the American Chemical Society

DOI: 10.1021/ja302788c

One-electron Ni(II)/(I) redox couple: potential role in hydrogen activation and production

One-electron Ni(II)/(I) redox couple: potential role in hydrogen activation and production:

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30176H, Communication

Stephen J. Tereniak, Elodie E. Marlier, Connie C. Lu
The complementary reactions of forming and activating hydrogen are studied using a nickel system with a wide bite-angle diphosphine ligand.
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