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Molecular Catalysts with Diphosphine Ligands Containing Pendant Amines

Journal Article · · Chemical Reviews
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
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Pendant amines play an invaluable role in chemical reactivity, especially for molecular catalysts based on Earth-abundant metals. As inspired by [FeFe]-hydrogenases, which contain a pendant amine positioned for cooperative bifunctionality, synthetic catalysts have been developed to emulate this multifunctionality through incorporation of a pendant amine in the second coordination sphere. Cyclic diphosphine ligands containing two amines serve as the basis for a class of catalysts that have been extensively studied and used to demonstrate the impact of a pendant base. These 1,5-diaza-3,7-diphosphacyclooctanes, now often referred to as “P2N2” ligands, have profound effects on the reactivity of many catalysts. The resulting [Ni(PR2NR´2)2]2+ complexes are electrocatalysts for both the oxidation and production of H2. Achieving the optimal benefit of the pendant amine requires that it has suitable basicity and is properly positioned relative to the metal center. In addition to the catalytic efficacy demonstrated with [Ni(PR2NR´2)2]2+ complexes for the oxidation and production of H2, catalysts with diphosphine ligands containing pendant amines have also be demonstrated for a variety of metals for many different reactions, both in solution and immobilized on surfaces. Here, the impact of pendant amines in catalyst design has been demonstrated and continues to expand.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1922077
Report Number(s):
PNNL-SA-168825
Journal Information:
Chemical Reviews, Journal Name: Chemical Reviews Journal Issue: 14 Vol. 122; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Synthesis, Structures, and Reactions of Manganese Complexes Containing Diphosphine Ligands with Pendant Amines journal October 2010
Comprehensive Thermodynamics of Nickel Hydride Bis(Diphosphine) Complexes: A Predictive Model through Computations journal November 2011
Stabilization of Nickel Complexes with Ni 0 ···H–N Bonding Interactions Using Sterically Demanding Cyclic Diphosphine Ligands journal December 2011
Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base journal September 2012
Synthesis, Structural, and Electrocatalytic Reduction Studies of [Pd(P 2 N 2 ) 2 ] 2+ Complexes journal August 2013
Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation journal November 2013
Comparison of [Ni(P Ph 2 N Ph 2 ) 2 (CH 3 CN)] 2+ and [Pd(P Ph 2 N Ph 2 ) 2 ] 2+ as Electrocatalysts for H 2 Production journal January 2014
Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H 2 Production journal June 2014
Calculated Hydride Donor Abilities of Five-Coordinate Transition Metal Hydrides [HM(diphosphine) 2 ] + (M = Ni, Pd, Pt) as a Function of the Bite Angle and Twist Angle of Diphosphine Ligands journal June 2008
Biomimetic assembly and activation of [FeFe]-hydrogenases journal June 2013
Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase journal October 2011
Nickel-centred proton reduction catalysis in a model of [NiFe] hydrogenase journal July 2016
Spontaneous activation of [FeFe]-hydrogenases by an inorganic [2Fe] active site mimic journal August 2013
Ni-Zn-[Fe4-S4] and Ni-Ni-[Fe4-S4] clusters in closed and open α subunits of acetyl-CoA synthase/carbon monoxide dehydrogenase journal March 2003
Dual properties of a hydrogen oxidation Ni-catalyst entrapped within a polymer promote self-defense against oxygen journal February 2018
Designing electrochemically reversible H2 oxidation and production catalysts journal August 2018
Reversible catalysis journal April 2021
Novel chiral 1,5-diaza-3,7-diphosphacyclooctane ligands and their transition metal complexes journal January 2003
A key step in the formation of acrylic acid from CO2and ethylene: the transformation of a nickelalactone into a nickel-acrylate complex journal January 2006
The roles of the first and second coordination spheres in the design of molecular catalysts for H 2 production and oxidation journal January 2009
Diiron species containing a cyclic PPh2NPh2diphosphine related to the [FeFe]H2ases active site journal January 2011
A proton channel allows a hydrogen oxidation catalyst to operate at a moderate overpotential with water acting as a base journal January 2014
Controlling proton movement: electrocatalytic oxidation of hydrogen by a nickel( ii ) complex containing proton relays in the second and outer coordination spheres journal January 2014
Solvent and electrolyte effects on Ni(P R 2 N R′ 2 ) 2 -catalyzed electrochemical oxidation of hydrogen journal January 2014
Proton reduction by molecular catalysts in water under demanding atmospheres journal January 2014
Electrochemical oxidation of H 2 catalyzed by ruthenium hydride complexes bearing P 2 N 2 ligands with pendant amines as proton relays journal January 2014
Toward the rational benchmarking of homogeneous H 2 -evolving catalysts journal January 2014
Electrocatalytic H 2 production with a turnover frequency >10 7 s −1 : the medium provides an increase in rate but not overpotential journal January 2014
Heterolytic cleavage of H 2 by bifunctional manganese( i ) complexes: impact of ligand dynamics, electrophilicity, and base positioning journal January 2014
Hydrogenation of carbon dioxide to methanol using a homogeneous ruthenium–Triphos catalyst: from mechanistic investigations to multiphase catalysis journal January 2015
A noble metal-free proton-exchange membrane fuel cell based on bio-inspired molecular catalysts journal January 2015
Nickel phosphine catalysts with pendant amines for electrocatalytic oxidation of alcohols journal January 2015
Photoelectrochemical operation of a surface-bound, nickel-phosphine H 2 evolution catalyst on p-Si(111): a molecular semiconductor|catalyst construct journal January 2015
Covalent attachment of diphosphine ligands to glassy carbon electrodes via Cu-catalyzed alkyne-azide cycloaddition. Metallation with Ni( ii ) journal January 2015
Water-assisted proton delivery and removal in bio-inspired hydrogen production catalysts journal January 2015
Photoswitching a molecular catalyst to regulate CO2 hydrogenation journal January 2015
Oxygen-tolerant proton reduction catalysis: much O 2 about nothing? journal January 2015
Bio-inspired noble metal-free nanomaterials approaching platinum performances for H 2 evolution and uptake journal January 2016
Increasing the rate of hydrogen oxidation without increasing the overpotential: a bio-inspired iron molecular electrocatalyst with an outer coordination sphere proton relay journal January 2015
Molecular engineered nanomaterials for catalytic hydrogen evolution and oxidation journal January 2016
Evaluating the role of acidic, basic, and polar amino acids and dipeptides on a molecular electrocatalyst for H 2 oxidation journal January 2017
Optimizing conditions for utilization of an H 2 oxidation catalyst with outer coordination sphere functionalities journal January 2016
Photogeneration of hydrogen from water by a robust dye-sensitized photocathode journal January 2016
Light-driven hydrogen production from aqueous solutions based on a new Dubois-type nickel catalyst journal January 2017
Evaluating the impacts of amino acids in the second and outer coordination spheres of Rh-bis(diphosphine) complexes for CO 2 hydrogenation journal January 2019
Promoting proton coupled electron transfer in redox catalysts through molecular design journal January 2019
Identifying high-performance catalytic conditions for carbon dioxide reduction to dimethoxymethane by multivariate modelling journal January 2019
Thermodynamic and kinetic hydricity of transition metal hydrides journal January 2020
[FeFe]-Hydrogenases: maturation and reactivity of enzymatic systems and overview of biomimetic models journal January 2021
Redox mediators accelerate electrochemically-driven solubility cycling of molecular transition metal complexes journal January 2020
A protein scaffold enables hydrogen evolution for a Ni-bisdiphosphine complex journal January 2021
How do H2 oxidation molecular catalysts assemble onto carbon nanotube electrodes? A crosstalk between electrochemical and multi-physical characterization techniques journal January 2021
Homogeneous ruthenium catalyzed hydrogenation of esters to alcohols‡ journal January 1998
The synthesis of amines by the homogeneous hydrogenation of secondary and primary amides journal January 2007
Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere journal January 2008
A proton–hydride diiron complex with a base-containing diphosphine ligand relevant to the [FeFe]-hydrogenase active site journal January 2008
14N HYSCORE investigation of the H-cluster of [FeFe] hydrogenase: evidence for a nitrogen in the dithiol bridge journal January 2009
Reduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines journal January 2010
Hydrogen oxidation catalysis by a nickel diphosphine complex with pendant tert-butyl amines journal January 2010
Theoretical studies of the mechanism of catalytic hydrogen production by a cobaloxime journal January 2011
A rare terminal dinitrogen complex of chromium journal January 2011
Formate oxidation via β-deprotonation in [Ni(PR2NR′2)2(CH3CN)]2+ complexes journal January 2012
Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy journal January 2012
Thermally stable N2 and H2 adducts of cationic nickel(ii) journal January 2012
Production of H2 at fast rates using a nickel electrocatalyst in water–acetonitrile solutions journal January 2013
Voltammetric and spectroscopic characterization of early intermediates in the Co(ii)–polypyridyl-catalyzed reduction of water journal January 2013
Standard Electrode Potentials and Temperature Coefficients in Water at 298.15 K journal January 1989
Nature of hydrogen interactions with Ni(II) complexes containing cyclic phosphine ligands with pendant nitrogen bases journal March 2007
Agostic interactions in transition metal compounds journal April 2007
Reversibility and efficiency in electrocatalytic energy conversion and lessons from enzymes journal August 2011
Insights into proton-coupled electron transfer mechanisms of electrocatalytic H2 oxidation and production journal April 2012
Acidic ionic liquid/water solution as both medium and proton source for electrocatalytic H2 evolution by [Ni(P2N2)2]2+ complexes journal June 2012
Role of pendant proton relays and proton-coupled electron transfer on the hydrogen evolution reaction by nickel hangman porphyrins journal October 2014
Amino acid modified Ni catalyst exhibits reversible H 2 oxidation/production over a broad pH range at elevated temperatures journal November 2014
Investigating the role of chain and linker length on the catalytic activity of an H 2 production catalyst containing a β-hairpin peptide journal June 2016
Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes
  • Bullock, R. Morris; Chambers, Geoffrey M.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 375, Issue 2101 https://doi.org/10.1098/rsta.2017.0002
journal July 2017
On the concept of frustrated Lewis pairs
  • Fontaine, Frédéric-Georges; Stephan, Douglas W.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 375, Issue 2101 https://doi.org/10.1098/rsta.2017.0004
journal July 2017
A Ni-Fe-Cu Center in a Bifunctional Carbon Monoxide Dehydrogenase/ Acetyl-CoA Synthase journal October 2002
From Hydrogenases to Noble Metal-Free Catalytic Nanomaterials for H2 Production and Uptake journal December 2009
A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s-1 for H2 Production journal August 2011
X-ray Crystal Structure of the Fe-Only Hydrogenase (CpI) from Clostridium pasteurianum to 1.8 Angstrom Resolution journal December 1998
The broadening reach of frustrated Lewis pair chemistry journal December 2016
Using nature’s blueprint to expand catalysis with Earth-abundant metals journal August 2020
Electrolyte Formulations Based on Dinitrile Solvents for High Voltage Li-Ion Batteries journal January 2013
Catalytic Fixation of Carbon Dioxide to Formic acid by Transition-Metal Complexes Under mild Conditions journal August 1976
Revisiting the Terawatt Challenge journal March 2020
Future Global Energy Prosperity: The Terawatt Challenge journal June 2005

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Amines
Catalysts
Ligands
Metals
Oxidation