Selective Electrocatalytic Reduction of CO2 to Formate by Water-Stable Iridium Dihydride Pincer Complexes

Selective Electrocatalytic
Reduction of CO2 to Formate by Water-Stable Iridium Dihydride
Pincer Complexes:

Journal of the American Chemical Society

DOI: 10.1021/ja300543s

Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays

Electrocatalytic Oxygen
Reduction by Iron Tetra-arylporphyrins
Bearing Pendant Proton Relays:

Journal of the American Chemical Society

DOI: 10.1021/ja211987f

Lewis Acid Base Reactions between Boron Trifluoride and Complex Oxoanions as a Versatile Access to Fluorooxoanions: Synthesis of Sodium (Trifluoroborato)sulfate

Lewis Acid Base Reactions between Boron Trifluoride and Complex Oxoanions as a Versatile Access to Fluorooxoanions: Synthesis of Sodium (Trifluoroborato)sulfate:

Abstract Na₂SO₄BF₃, synthesized in a closed vessel from BF₃ and Na₂SO₄ at 603 K, crystallizes in the triclinic space group P (a = 6.6033(2), b = 6.6328(2), c = 6.6349 (1) Å, α = 84.542(2), β = 84.458(1) and γ = 65.762(1)°). The novel fluorooxo anion [SO₄BF₃]^2– displays a structure similar to the disulfate anion S₂O₇^2–. Heating the title compound in the absence of BF₃ in the gas phase leads to decomposition even at 553 K, which is below the temperature of synthesis under BF₃ pressure.

Synthesis, crystal structure, spectroscopic and electrochemical properties, and H2-evolving activity of a new [PtCl(terpyridine)]+ derivative with viologen-like redox properties

Synthesis, crystal structure, spectroscopic and electrochemical properties, and H2-evolving activity of a new [PtCl(terpyridine)]+ derivative with viologen-like redox properties:

Dalton Trans., 2012, Advance Article DOI: 10.1039/C2DT12209J, Paper

Masayuki Kobayashi, Shigeyuki Masaoka, Ken Sakai
A new Pt(II)-based metalloviologen as an H₂-evolving catalyst was developed, and its electrochemical and photochemical properties were investigated.

Enantiopure C1-Symmetric Bis(imino)pyridine Cobalt Complexes for Asymmetric Alkene Hydrogenation

Enantiopure C1-Symmetric
Bis(imino)pyridine Cobalt Complexes for Asymmetric Alkene Hydrogenation:

Journal of the American Chemical Society

DOI: 10.1021/ja300503k

Mechanisms for CO Production from CO2 Using Reduced Rhenium Tricarbonyl Catalysts

Mechanisms for CO Production
from CO2 Using
Reduced Rhenium Tricarbonyl Catalysts:

Journal of the American Chemical Society

DOI: 10.1021/ja2105834

Reversible H2 Addition across a Nickel–Borane Unit as a Promising Strategy for Catalysis

Reversible H2 Addition across a Nickel–Borane
Unit as a Promising Strategy for Catalysis:

Journal of the American Chemical Society

DOI: 10.1021/ja211419t

A 4,5-Diphosphino-Substituted Imidazolium Salt: A Building Block for the Modular Synthesis of Mixed Diphosphine–NHC Heterometallic Complexes

A 4,5-Diphosphino-Substituted Imidazolium Salt: A Building Block for the Modular Synthesis of Mixed Diphosphine–NHC Heterometallic Complexes:

Fused in the same molecule! An N-heterocyclic carbene and a diphosphine are generated and used in the modular synthesis of a variety of target heterometallic complexes. The experimental approach involves formation of a unique 4,5-bis(diphenylphosphino)-1,3-dimethyl-imidazolium salt, simply by starting from 1-methylimidazole (see scheme; M¹=Cr, Mn; M²=Au, Rh, Pd; LiHMDS=LiN(SiMe₃)₂).

Chem. Eur. J

Molybdenum-catalyzed reduction of molecular dinitrogen under mild reaction conditions

Molybdenum-catalyzed reduction of molecular dinitrogen under mild reaction conditions:

Dalton Trans., 2012, Accepted Manuscript
DOI: 10.1039/C2DT30105A, Perspective

Yoshiaki Nishibayashi
Quite recently, we have found two nitrogen fixation systems catalyzed by the molybdenum-dinitrogen complexes under mild reaction conditions; one is the transformation of molecular dinitrogen into its synthetic equivalent of...

Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals

Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals:

Abstract

In view of the diminishing oil resources and the ongoing climate change, the use of efficient and environmentally benign technologies for the utilization of renewable resources has become indispensible. Therein, hydrogenolysis reactions offer a promising possibility for future biorefinery concepts. These reactions result in the cleavage of CC and CO bonds by hydrogen and allow direct access to valuable platform chemicals already integrated in today’s value chains. Thus, hydrogenolysis bears the potential to bridge currently available technologies and future biomass-based refinery concepts. This Review highlights past and present developments in this field, with special emphasis on the direct utilization of cellulosic feedstocks.

Hydrogenolysis of renewable feedstocks allows direct access to valuable platform chemicals already integrated in today’s value chains. Transformations based on hydrogenolysis bear the potential to bridge available technologies and future biorefinery concepts. This Review highlights developments in this field, with special emphasis on the direct transformation of cellulose and sugars.

Activation of H–Hand H–O Bonds at Phosphoruswith Diiron Complexes Bearing Pyramidal Phosphinidene Ligands

Activation of H–H
and H–O Bonds at Phosphorus
with Diiron Complexes Bearing Pyramidal Phosphinidene Ligands:

Inorganic Chemistry

DOI: 10.1021/ic2026945

Simple Ligand Effects Switch a Hydrogenase Mimic between H2 and O2 Activation

Simple Ligand Effects Switch a Hydrogenase Mimic between H2 and O2 Activation:

Abstract

Herein, we report a [NiRu] biomimetic system for O₂-tolerant [NiFe]hydrogenases and demonstrate that electron donation to the [NiRu] center can switch the system between the activation of H₂ and O₂ through simple ligand effects by using hexamethylbenzene and pentamethylcyclopentadienyl ligands, respectively. Furthermore, we present the synthesis and direct observations of a [NiRu]–peroxo species, which was formed by the oxygenation of a Ni-SIa model [NiRu] complex, that we propose as a biomimetic analogue of O₂-bound species (OBS) of O₂-tolerant [NiFe]hydrogenases. The [NiRu]–peroxo complex was fully characterized by X-ray analysis, X-ray photoelectron spectroscopy (XPS), mass spectrometry, and ¹H NMR spectroscopy. The OBS analogue was capable of oxidizing p-hydroquinone and sodium borohydride to turn back into the Ni-SIa model complex.

At the flick of a switch: A [NiRu] biomimetic system for O₂-tolerant [NiFe]hydrogenases was constructed. Electron donation to the [NiRu] center switched the system between activation of H₂ and O₂. Furthermore, a [NiRu]–peroxo species, which was capable of oxidizing p-hydroquinone, was considered as a biomimetic analogue of O₂-bound species (OBS) of O₂-tolerant [NiFe]hydrogenases.

Characterization of the FeH Bond in a Three-Coordinate Terminal Hydride Complex of Iron(I)

Characterization of the Fe<img src="http://onlinelibrarystatic.wiley.com/undisplayable_characters/00f8ff.gif" alt="[BOND]">H Bond in a Three-Coordinate Terminal Hydride Complex of Iron(I):

Three’s company: Iron(I) hydride complexes are presented (see picture; N blue, O red) that are the first monomeric open-shell hydride complexes to be crystallographically verified as being three-coordinate at the metal. Backbonding into diketiminate π* orbitals stabilizes the low oxidation state. The FeH bonding has been analyzed using electron-nuclear double resonance (ENDOR).

Unsensitized PhotochemicalHydrogen Production Catalyzedby Diiron Hydrides

Unsensitized Photochemical
Hydrogen Production Catalyzed
by Diiron Hydrides:

Journal of the American Chemical Society

DOI: 10.1021/ja211778j

Hydrogenases and oxygen

Hydrogenases and oxygen:

Chem. Sci., 2012, Advance Article
DOI: 10.1039/C2SC01112C, Perspective

Martin Tillmann Stiebritz, Markus Reiher
We summarize the current picture of oxygen-induced inhibition of the different classes of hydrogenases and discuss possible avenues that might lead to tailored oxygen-robust enzyme variants.
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Synthesis, Reactivity, and Catalytic Application of a Nickel Pincer Hydride Complex

Synthesis, Reactivity,
and Catalytic Application of
a Nickel Pincer Hydride Complex:

Organometallics DOI: 10.1021/om201279j

Xile Hu

Electronic structures of methylated azaferrocenes and their borane adducts: Photoelectron spectroscopy and electronic structure calculations

Electronic structures of methylated azaferrocenes and their borane adducts: Photoelectron spectroscopy and electronic structure calculations:

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12237E, Paper

Tim J. Brunker, Branka Kovac, Konrad Kowalski, Walther Polit, Rainer F. Winter, Arnold L. Rheingold, Igor Novak
Azaferrocenes, borane adducts, photoelectron spectroscopy.

Synthesis, structure, and physical properties for a series of trigonal bipyramidal MII-Cl complexes with intramolecular hydrogen bonds

Synthesis, structure, and physical properties for a series of trigonal bipyramidal MII-Cl complexes with intramolecular hydrogen bonds:

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12244H, Paper

Nathaniel S. Sickerman, Young Jun Park, Gary K.-Y. Ng, Jefferson E. Bates, Mark Hilkert, Joseph W. Ziller, Filipp Furche, A. S. Borovik
The tripodal ligand tris(2-amino-oxazoline)amine stabilizes a series of monomeric M^II-Cl complexes.

Access to catenated and branched polyphosphorus ligands and coordination complexes via a tri(pyrazolyl)phosphane

Access to catenated and branched polyphosphorus ligands and coordination complexes via a tri(pyrazolyl)phosphane:

Chem. Commun., 2012, Advance Article DOI: 10.1039/C2CC18030H, Communication

Kai-Oliver Feldmann, Roland Frohlich, Jan J. Weigand
We report a high yielding, one-pot synthesis of a tri- and an iso-tetraphosphane from a readily accessible tri(pyrazolyl)phosphane. Their potential as ligands has been shown in complexes with the Fe(CO)₄-fragment.

Efficient dynamic kinetic resolution of racemic secondary alcohols by a chemoenzymatic system using bifunctional iridium complexes with C-N chelate amido ligands

Efficient dynamic kinetic resolution of racemic secondary alcohols by a chemoenzymatic system using bifunctional iridium complexes with C-N chelate amido ligands:

Chem. Commun., 2012, Accepted Manuscript
DOI: 10.1039/C2CC30333G, Communication

Yasuhiro Sato, Yoshihito Kayaki, Takao Ikariya
The combined catalyst system of bifunctional amidoiridium complexes derived from benzylic amines with CALB was found to provide a range of chiral acetates from racemic secondary alcohols in excellent yields...

Dehydrogenative Oxidationof Alcohols in Aqueous MediaUsing Water-Soluble and Reusable Cp*Ir Catalysts Bearing a FunctionalBipyridine Ligand

Dehydrogenative Oxidation
of Alcohols in Aqueous Media
Using Water-Soluble and Reusable Cp*Ir Catalysts Bearing a Functional
Bipyridine Ligand:

Journal of the American Chemical Society

DOI: 10.1021/ja210857z

Dioxygen Reactivity of New Bispidine-Copper Complexes

Dioxygen Reactivity of
New Bispidine-Copper Complexes:

Inorganic ChemistryDOI: 10.1021/ic2019296

Karlin et al

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic:

An efficient ligand combination: A new bis(diphosphine) nickel(II) complex (see picture) is described. A ΔG° value of 0.84 kcal mol⁻¹ for hydrogen addition for this complex was calculated from the experimentally determined equilibrium constant. This complex displayed a reversible electrocatalytic activity for hydrogen production and oxidation at low overpotentials, which are characteristic for hydrogenase enzymes.

Oxidative Addition Reactions of Bis-Aminophosphine and Bis-Phosphinite Nickel(0) Pincer Complexes

Oxidative Addition Reactions
of Bis-Aminophosphine
and Bis-Phosphinite Nickel(0) Pincer Complexes:

Organometallics DOI: 10.1021/om201229x

Doug Stephan

Aerobic CO Oxidation of a Metal-Bound Carbonyl in a NHC-Stabilized Cobalt Half-Sandwich Complex

Aerobic CO Oxidation of
a Metal-Bound Carbonyl in
a NHC-Stabilized Cobalt Half-Sandwich Complex:

Organometallics DOI: 10.1021/om201037w

Rhenium(V) and Technetium(V) Nitrido Complexes with Mixed Tridentate π-Donor and Monodentate π-Acceptor Ligands

Rhenium(V) and Technetium(V)
Nitrido Complexes with
Mixed Tridentate π-Donor and Monodentate π-Acceptor Ligands:

Inorganic Chemistry DOI: 10.1021/ic202605z

suitable ligand for Ni-Fe models?

Novel access to carbodiphosphoranes in the coordination sphere of group 10 metals: template synthesis and protonation of PCP pincer carbodiphosphorane complexes of C(dppm)2

Novel access to carbodiphosphoranes in the coordination sphere of group 10 metals: template synthesis and protonation of PCP pincer carbodiphosphorane complexes of C(dppm)2:

Dalton Trans., 2012, Advance Article DOI: 10.1039/C2DT11949H, Paper

Christian Reitsamer, Silvia Stallinger, Walter Schuh, Holger Kopacka, Klaus Wurst, Dagmar Obendorf, Paul Peringer
The pincer carbodiphosphorane complexes [M(Cl)(C(dppm)₂-[small kappa]3P,C,P)]Cl are synthesized from MCl₂, dppm and CS₂ as the source of the central CDP carbon.

Pincers seem to help CO2 fixation

Highly active zinc alkyl cations for the controlled and immortal ring-opening polymerization of [varepsilon]-caprolactone

Highly active zinc alkyl cations for the controlled and immortal ring-opening polymerization of [varepsilon]-caprolactone:

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12336C, Communication

Charles Romain, Vitor Rosa, Christophe Fliedel, Frederic Bier, Frederic Hild, Richard Welter, Samuel Dagorne, Teresa Aviles
Novel zinc cations are highly active in the immortal ROP of [varepsilon]-caprolactone to yield narrowly disperse and chain-length-controlled poly([varepsilon]-caprolactone), whether in solution or bulk polymerization.

NIL on Zn

Tuning redox potentials of bis(imino)pyridine cobalt complexes: an experimental and theoretical study involving solvent and ligand effects

Tuning redox potentials of bis(imino)pyridine cobalt complexes: an experimental and theoretical study involving solvent and ligand effects:

Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12195F, Paper C. Moyses Araujo, Mark D. Doherty, Steven J. Konezny, Oana R. Luca, Alex Usyatinsky, Hans Grade, Emil Lobkovsky, Grigorii L. Soloveichik, Robert H. Crabtree, Victor S. Batista

CV measurements and DFT/B3LYP calculations show that in solution a series of (NNN)CoCl₂ complexes exist in equilibrium with [(NNN)₂Co][CoCl₄] which exhibit Co^II/III oxidation potentials spanning nearly 750 mV in acetonitrile.