Tuesday, October 30, 2012

Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas:

Abstract

A new iridium-catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe=cyclooctene) and racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (rac-BINAP) in a mesitylene solution saturated with water. A catalytic amount of lithium chloride was also added to improve the catalyst turnover. The reaction has been applied to a variety of primary alcohols and gives rise to products in good to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation of the primary alcohol to the corresponding aldehyde takes place, which is then followed by decarbonylation to the product with one less carbon atom.
Thumbnail image of graphical abstract
Step on the syngas! An iridium catalyst promotes two transformations in the same pot by cleaving both molecular hydrogen and carbon monoxide from primary alcohols (see scheme). The reaction does not require any stoichiometric additives and tolerates a variety of functional groups.

Symmetrical Hydrogen Bondsin Iridium(III) Alkoxideswith Relevance to Outer Sphere Hydrogen Transfer

Symmetrical Hydrogen Bonds
in Iridium(III) Alkoxides
with Relevance to Outer Sphere Hydrogen Transfer
:
TOC Graphic
Inorganic Chemistry
DOI: 10.1021/ic301601c

Highly ChemoselectiveMetal-Free Reduction of PhosphineOxides to Phosphines

Highly Chemoselective
Metal-Free Reduction of Phosphine
Oxides to Phosphines
:
TOC Graphic
Journal of the American Chemical Society
DOI: 10.1021/ja3069165

Involvement of Tyr108in the Enzyme Mechanism of theSmall Laccase from Streptomyces coelicolor

Involvement of Tyr108
in the Enzyme Mechanism of the
Small Laccase from Streptomyces coelicolor
:
TOC Graphic
Journal of the American Chemical Society
DOI: 10.1021/ja3088604

Friday, October 26, 2012

Identification and Characterization of the “Super-Reduced” State of the H-Cluster in [FeFe] Hydrogenase: A New Building Block for the Catalytic Cycle?

Identification and Characterization of the “Super-Reduced” State of the H-Cluster in [FeFe] Hydrogenase: A New Building Block for the Catalytic Cycle?: Thumbnail image of graphical abstract
Super-reduced and super-active: A new redox state in the active site of algal [FeFe] hydrogenases has been identified and characterized by EPR and FTIR spectroscopy. Electrochemical and in vitro essays show that this species is highly active in hydrogen production and suggest that it is a key intermediate in the catalytic cycle of all [FeFe] hydrogenases.

Tuesday, October 23, 2012

100 years of the hydrogen bond

100 years of the hydrogen bond:
Nature Chemistry 4, 863 (2012).
doi:10.1038/nchem.1482

Author: Patrick Goymer
For Patrick Goymer, the story behind the scientists who first described the phenomenon known as hydrogen bonding is a familiar one.

Alteration of the oxygen-dependent reactivity of de novo Due Ferri proteins

Alteration of the oxygen-dependent reactivity of de novo Due Ferri proteins:

Nature Chemistry 4, 900 (2012).
doi:10.1038/nchem.1454

Authors: Amanda J. Reig, Marcos M. Pires, Rae Ana Snyder, Yibing Wu, Hyunil Jo, Daniel W. Kulp, Susan E. Butch, Jennifer R. Calhoun, Thomas G. Szyperski, Edward I. Solomon & William F. DeGrado
Representing the first successful rational reprogramming of function in a de novo protein, the reactivity of a designed di-iron carboxylate protein from the Due Ferri family was altered from hydroquinone oxidation to arylamine N-hydroxylation through the introduction of a critical third histidine ligand in the active site.

Sunday, October 21, 2012

Synthesis, characterization, and electrochemical properties of diiron propaneditellurolate (PDTe) complexes as the active site models of [FeFe]-hydrogenases

Synthesis, characterization, and electrochemical properties of diiron propaneditellurolate (PDTe) complexes as the active site models of [FeFe]-hydrogenases:
Dalton Trans., 2012, Accepted Manuscript
DOI: 10.1039/C2DT31976D, Paper
Li-Cheng Song, Qianli Li, Zhan-Heng Feng, Xiao-Jing Sun, Zhao-Jun Xie, Haibin Song
Parent complex ([small mu ]-PDTe)Fe2(CO)6 (1, PDTe = [small mu ]-TeCH2CH2CH2Te-[small mu ]) is prepared via a new synthetic route involving reaction of ([small mu ]-Te2)Fe2(CO)6 with Et3BHLi, followed by treatment of ([small mu ]-LiTe)2Fe2(CO)6 with Br(CH2)3Br in 43% yield....
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Saturday, October 20, 2012

Synthesis, characterization, and electrochemical properties of diiron propaneditellurolate (PDTe) complexes as the active site models of [FeFe]-hydrogenases

Synthesis, characterization, and electrochemical properties of diiron propaneditellurolate (PDTe) complexes as the active site models of [FeFe]-hydrogenases:
Dalton Trans., 2012, Accepted Manuscript
DOI: 10.1039/C2DT31976D, Paper
Li-Cheng Song, Qianli Li, Zhan-Heng Feng, Xiao-Jing Sun, Zhao-Jun Xie, Haibin Song
Parent complex ([small mu ]-PDTe)Fe2(CO)6 (1, PDTe = [small mu ]-TeCH2CH2CH2Te-[small mu ]) is prepared via a new synthetic route involving reaction of ([small mu ]-Te2)Fe2(CO)6 with Et3BHLi, followed by treatment of ([small mu ]-LiTe)2Fe2(CO)6 with Br(CH2)3Br in 43% yield....
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Friday, October 19, 2012

Thursday, October 18, 2012

Iron-Catalyzed Polymerization of Isoprene and Other 1,3-Dienes

Iron-Catalyzed Polymerization of Isoprene and Other 1,3-Dienes: Thumbnail image of graphical abstract
Ironing rubber: Iminopyridine-based FeCl2 catalysts catalyze the polymerization of 1,3-dienes and provide stereoselective access to elastomers such as polyisoprenes, polymyrcenes, and polyfarnesenes. The choice of ligand determines the double-bond geometry in the polymer repeating unit, which can be varied from trans/cis >99:1 to <1:99 (see scheme).

Monday, October 15, 2012

The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds

The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds:
Chem. Commun., 2012, Advance Article
DOI: 10.1039/C2CC35304K, Feature Article
Jennifer C. Green, Malcolm L. H. Green, Gerard Parkin
3-Centre 2-electron (3c-2e) interactions can be classified according to whether the pair of electrons are provided by two atoms (Class I) or by one atom (Class II). Recognizing that compounds with symmetrically bridging carbonyl ligands can belong to Class II provides a simple rationalization of the absence of M-M bonds in molecules such as Fe2(CO)9 and [CpFe(CO)2].
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Synthesis, Structure, and Characterization of DinuclearCopper(I) Halide Complexes with P^N Ligands Featuring Exciting PhotoluminescenceProperties

Synthesis, Structure, and Characterization of Dinuclear
Copper(I) Halide Complexes with P^N Ligands Featuring Exciting Photoluminescence
Properties
:
TOC Graphic
Inorganic Chemistry
DOI: 10.1021/ic300979c

Synthesis and Reactivityof Nickel Hydride Complexesof an α-Diimine Ligand

Synthesis and Reactivity
of Nickel Hydride Complexes
of an α-Diimine Ligand
:
TOC Graphic
Inorganic Chemistry
DOI: 10.1021/ic301392p

Saturday, October 13, 2012

The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds

The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds:
Chem. Commun., 2012, Advance Article
DOI: 10.1039/C2CC35304K, Feature Article
Jennifer C. Green, Malcolm L. H. Green, Gerard Parkin
3-Centre 2-electron (3c-2e) interactions can be classified according to whether the pair of electrons are provided by two atoms (Class I) or by one atom (Class II). Recognizing that compounds with symmetrically bridging carbonyl ligands can belong to Class II provides a simple rationalization of the absence of M-M bonds in molecules such as Fe2(CO)9 and [CpFe(CO)2].
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Saturday, October 6, 2012

[Report] A Local Proton Source Enhances CO2 Electroreduction to CO by a Molecular Fe Catalyst

[Report] A Local Proton Source Enhances CO2 Electroreduction to CO by a Molecular Fe Catalyst: Phenol groups in an iron complex appear to facilitate catalysis of carbon dioxide reduction by supplying protons.

Authors: Cyrille Costentin, Samuel Drouet, Marc Robert, Jean-Michel Savéant

Thursday, October 4, 2012

Frustrated Lewis Pair Inspired Carbon Dioxide Reduction by a Ruthenium Tris(aminophosphine) Complex

Frustrated Lewis Pair Inspired Carbon Dioxide Reduction by a Ruthenium Tris(aminophosphine) Complex: Thumbnail image of graphical abstract
Frustrating ruthenium: The ruthenium complex 1 is shown to bind carbon dioxide or aldehyde in a manner similar to a frustrated Lewis pair. Compound 2 catalyzes the reduction of CO2 in the presence of pinacolborane (HBpin), yielding MeOBpin and O(Bpin)2 (see picture; Ru red, P orange, N green, O light red, C black).

Tuesday, October 2, 2012

A Binuclear Iron–Thiolate Catalyst for Electrochemical Hydrogen Production in Aqueous Micellar Solution

A Binuclear Iron–Thiolate Catalyst for Electrochemical Hydrogen Production in Aqueous Micellar Solution:

Abstract

The substituted iron–thiolate complex [Fe2(μ-bdt)(CO)4{P(OMe)3}2] (bdt=benzenedithiolate) is an active catalyst for electrochemical hydrogen production in aqueous sodium dodecyl sulfate solution, with a high apparent rate constant of 4×106 M−1 s−1. The half-peak potential for catalysis of proton reduction is less negative than −0.6 V versus the standard hydrogen electrode at pH 3. Voltammetric data are consistent with the rate of electrode reaction controlled by diffusion. A mechanism that begins with the rapid protonation of the iron–thiolate catalyst is proposed. The Faradaic efficiency in diluted HCl solutions is close to 100 %, but the catalytic activity decayed after about twelve turnovers when electrolysis was carried out in the presence of acetic acid.
Thumbnail image of graphical abstract
Iron brew: [Fe2(μ-bdt)(CO)4{P(OMe)3}2] (bdt=benzenedithiolate) catalyzes electrochemical hydrogen production in an aqueous micellar solution (see scheme). It achieves a turnover frequency of 4400 s−1 at a potential less negative than −0.6 V (versus a standard hydrogen electrode) at pH 3.

Multielectron-Transfer Templates via Consecutive Two-Electron Transformations: Iron–Sulfur Complexes Relevant to Biological Enzymes

Multielectron-Transfer Templates via Consecutive Two-Electron Transformations: Iron–Sulfur Complexes Relevant to Biological Enzymes: Thumbnail image of graphical abstract
[FeFe] hydrogenase mimics: Two polynuclear iron–sulfur complexes (2 and 3; see figure) were prepared and structurally characterized. They are potentially effective and stable multielectron-transfer relays for mediating four- and six-electron transformations via a cascade of reversible two-electron redox steps with relatively narrow potential spans.