Towards a Comprehensive Hydride Donor Ability Scale

Towards a Comprehensive Hydride Donor Ability Scale:

Abstract

Rates of hydride transfer from several hydride donors to benzhydrylium ions have been measured at 20 °C and used for the determination of empirical nucleophilicity parameters N and s_N according to the linear free energy relationship log k_20 °C=s_N(N+E). Comparison of the rate constants of hydride abstraction by tritylium ions with those calculated from the reactivity parameters s_N, N, and E showed fair agreement. Therefore, it was possible to convert the large number of literature data on hydride abstraction by tritylium ions into N and s_N parameters for the corresponding hydride donors, and construct a reactivity scale for hydride donors covering more than 20 orders of magnitude.

The lineup for hydride donors spans more than 20 orders of magnitude in reactivity and is based on the kinetics of hydride-transfer reactions towards benzhydrylium (Ar₂CH⁺) and tritylium ions (Ar₃C⁺). Linear free energy relationships according to the correlation equation log k=s_N(N+E) showed that the electrophilicities E of these carbocations can be used for the determination of the hydrides’ nucleophilicity parameters N and s_N (see figure), the knowledge of which is expected to facilitate the selection of efficient reductants in organic syntheses.

ReversibleDouble Oxidation and Protonation of theNon-Innocent Bridge in a Nickel(II) Salophen Complex

Reversible
Double Oxidation and Protonation of the
Non-Innocent Bridge in a Nickel(II) Salophen Complex:

Inorganic Chemistry

DOI: 10.1021/ic301684h

Nickel-Catalyzed Reductive Hydroesterification ofStyrenes Using CO2 and MeOH

Nickel-Catalyzed Reductive Hydroesterification of
Styrenes Using CO2 and MeOH:

Organometallics

DOI: 10.1021/om300819d

Synthesis and chemistry of bis(triisopropylphosphine) nickel(I) and nickel(0) precursors

Synthesis and chemistry of bis(triisopropylphosphine) nickel(I) and nickel(0) precursors:

Dalton Trans., 2013, Advance Article
DOI: 10.1039/C2DT32008H, Paper

Robert Beck, Manar Shoshani, Jonathan Krasinkiewicz, Jillian A. Hatnean, Samuel A. Johnson
The Ni(I) complexes (ⁱPr₃P)₂NiX (3a-c), (where X = Cl, Br, I) and Ni(0) dinitrogen complex [(ⁱPr₃P)₂Ni]₂([small mu ]-[small eta]¹:[small eta]¹-N₂) (5) serve as convenient precursors for complexes such as (ⁱPr₃P)₂Ni([small eta]²-CO₂) (7), [(ⁱPr₃P)Ni([small mu ]-[small eta]¹:[small eta]²-CS₂)]₂ (9), [(ⁱPr₃P)Ni([small mu ]₂-PPh₂)]₂ (10), (ⁱPr₃P)₂Ni(SPh)(H) (11) and [(ⁱPr₃P)Ni([small mu ]₂-SPh)]₂ (12).
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Catalytic IntramolecularHydroamination with a Bifunctional Iridium Pyrazolato Complex: SubstrateScope and Mechanistic Elucidation

Catalytic Intramolecular
Hydroamination with a Bifunctional Iridium Pyrazolato Complex: Substrate
Scope and Mechanistic Elucidation:

Organometallics

DOI: 10.1021/om301063n

Self-Supporting Oxygen Reduction ElectrocatalystsMade from a Nitrogen-Rich Network Polymer

Self-Supporting Oxygen Reduction Electrocatalysts
Made from a Nitrogen-Rich Network Polymer:

Journal of the American Chemical Society

DOI: 10.1021/ja3085934

Correction to TurnoverNumbers, TurnoverFrequencies, and Overpotential in Molecular Catalysis of ElectrochemicalReactions. Cyclic Voltammetry and Preparative-Scale Electrolysis

Correction to Turnover
Numbers, Turnover
Frequencies, and Overpotential in Molecular Catalysis of Electrochemical
Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis:

Journal of the American Chemical Society

DOI: 10.1021/ja3106187

Cooperative Catalysis by Iridium Complexes with a Bipyridonate Ligand: Versatile Dehydrogenative Oxidation of Alcohols and Reversible Dehydrogenation–Hydrogenation between 2-Propanol and Acetone

Cooperative Catalysis by Iridium Complexes with a Bipyridonate Ligand: Versatile Dehydrogenative Oxidation of Alcohols and Reversible Dehydrogenation–Hydrogenation between 2-Propanol and Acetone:

Going into reverse: An efficient and versatile catalytic system for the dehydrogenative oxidation of alcohols under extremely mild conditions is developed using a Cp*Ir complex with bipyridonate ligand as catalyst (see scheme, Cp*=pentamethylcyclopentadienyl). Reversible and repetitive transformation between 2-propanol and acetone by catalytic dehydrogenation–hydrogenation is also achieved.

Observation of the FeCN and FeCO Vibrations in the Active Site of [NiFe] Hydrogenase by Nuclear Resonance Vibrational Spectroscopy

Observation of the Fe<img src="http://onlinelibrarystatic.wiley.com/undisplayable_characters/00f8ff.gif" alt="[BOND]">CN and Fe<img src="http://onlinelibrarystatic.wiley.com/undisplayable_characters/00f8ff.gif" alt="[BOND]">CO Vibrations in the Active Site of [NiFe] Hydrogenase by Nuclear Resonance Vibrational Spectroscopy:

Nuclear inelastic scattering of ⁵⁷Fe labeled [NiFe] hydrogenase is shown to give information on different states of the enzyme. It was thus possible to detect and assign FeCO and FeCN bending and stretching vibrations of the active site outside the spectral range of the FeS cluster normal modes.

Proton Delivery and Removalin [Ni(PR2NR′2)2]2+ Hydrogen Production and OxidationCatalysts

Proton Delivery and Removal
in [Ni(PR2NR′2)2]2+ Hydrogen Production and Oxidation
Catalysts:

Journal of the American Chemical Society

DOI: 10.1021/ja307413x

Light-Driven ElectronTransfer between a Photosensitizerand a Proton-Reducing Catalyst Co-adsorbed to NiO

Light-Driven Electron
Transfer between a Photosensitizer
and a Proton-Reducing Catalyst Co-adsorbed to NiO:

Journal of the American Chemical Society

DOI: 10.1021/ja3082268

Cyclic Voltammetric Studiesof Chlorine-SubstitutedDiiron Benzenedithiolato Hexacarbonyl Electrocatalysts Inspired bythe [FeFe]-Hydrogenase Active Site

Cyclic Voltammetric Studies
of Chlorine-Substituted
Diiron Benzenedithiolato Hexacarbonyl Electrocatalysts Inspired by
the [FeFe]-Hydrogenase Active Site:

Organometallics

DOI: 10.1021/om300938e

Change in Coordinationof NCN Pincer Iron ComplexesContaining Bis(oxazolinyl)phenyl Ligands

Change in Coordination
of NCN Pincer Iron Complexes
Containing Bis(oxazolinyl)phenyl Ligands:

Organometallics

DOI: 10.1021/om300901k

Synthesis, Structure, and Reactivity of a Nickel Dihydrogen Complex

Synthesis, Structure, and Reactivity of a Nickel Dihydrogen Complex:

Hydrogen activation by nickel: A tBuPCP pincer ligand facilitates formation of cationic Ni^II dihydrogen and terminal dinitrogen complexes. The compounds have been characterized by X-ray crystallography and NMR spectroscopy. Addition of base promotes heterolytic cleavage of H₂ to form the corresponding neutral hydride complex .

Synthesis, Structure, and Reactivity of a Nickel Dihydrogen Complex

Synthesis, Structure, and Reactivity of a Nickel Dihydrogen Complex:

Hydrogen activation by nickel: A tBuPCP pincer ligand facilitates formation of cationic Ni^II dihydrogen and terminal dinitrogen complexes. The compounds have been characterized by X-ray crystallography and NMR spectroscopy. Addition of base promotes heterolytic cleavage of H₂ to form the corresponding neutral hydride complex .

Experimental and ComputationalStudies of the Reaction of Carbon Dioxide with Pincer-Supported Nickeland Palladium Hydrides

Experimental and Computational
Studies of the Reaction of Carbon Dioxide with Pincer-Supported Nickel
and Palladium Hydrides:

Organometallics

DOI: 10.1021/om3008597

Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H2O2 from O2

Hydrogenation of a Rhodium Peroxido Complex by Formate Derivatives: Mechanistic Studies and the Catalytic Formation of H2O2 from O2:

Hydrogenation of dioxygen: The rhodium peroxido complex 1, which can be prepared from 2 and dioxygen, can be reduced with dihydrogen sources to yield hydrogen peroxide. In a catalytic experiment, hydrogen peroxide is produced from dioxygen and ammonium formate under ambient conditions in the presence of 1 (see scheme).

A biocatalytic hydrogenation of carboxylic acids

A biocatalytic hydrogenation of carboxylic acids:

Chem. Commun., 2012, Accepted Manuscript
DOI: 10.1039/C2CC36479D, Communication

Frank Hollmann, Yan Ni, Peter Leon Hagedoorn, Isabel W.C.E. Arends, Jian-He Xu
A chemoselective method for the reduction of carboxylic acids is presented. The hyperthermophile Pyrococcus furiosus catalyzes the hydrogenation of a broad range of carboxylic acids selectively to the corresponding primary...
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Synthesis and structures of transition metal pacman complexes of heteroditopic Schiff-base pyrrole macrocycles

Synthesis and structures of transition metal pacman complexes of heteroditopic Schiff-base pyrrole macrocycles:

Dalton Trans., 2012, 41,13815-13831
DOI: 10.1039/C2DT31850D, Paper

James W. Leeland, Colin Finn, Berengere Escuyer, Hiroyuki Kawaguchi, Gary S. Nichol, Alexandra M. Z. Slawin, Jason B. Love
Macrocycles that combine pyrrole-imine and amine ether donor compartments form Ti, V, Cr, Co, and Pd complexes that adopt Pacman structures that facilitate the in-cleft binding of water through coordination and hydrogen bonds.
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An Iron(II) Complex ofa Diamine-Bridged Bis-N-HeterocyclicCarbene

An Iron(II) Complex of
a Diamine-Bridged Bis-N-Heterocyclic
Carbene:

Organometallics

DOI: 10.1021/om300888q

Smaller Sulfur MoleculesPromise Better Lithium–SulfurBatteries

Smaller Sulfur Molecules
Promise Better Lithium–Sulfur
Batteries:

Journal of the American Chemical Society

DOI: 10.1021/ja308170k

Tandem Hydroformylation/Hydrogenationof Alkenes toNormal Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst

Tandem Hydroformylation/Hydrogenation
of Alkenes to
Normal Alcohols Using Rh/Ru Dual Catalyst or Ru Single Component Catalyst:

Journal of the American Chemical Society

DOI: 10.1021/ja307998h