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Title: Thermodynamic Hydricities of Biomimetic Organic Hydride Donors

Journal Article · · Journal of the American Chemical Society
 [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Bowling Green State Univ., Bowling Green, OH (United States)
  3. Univ. of Pittsburgh, Pittsburgh, PA (United States)

Here, thermodynamic hydricities (ΔGH) in acetonitrile and dimethyl sulfoxide have been calculated and experimentally measured for several metal-free hydride donors: NADH analogs (BNAH, CN-BNAH, Me-MNAH, HEH), methylene tetrahydromethanopterin analogs (BIMH, CAFH), acridine derivatives (Ph-AcrH, Me2N-AcrH, T-AcrH, 4OH, 2OH, 3NH), and a triarylmethane derivative (6OH). The calculated hydricity values, obtained using density functional theory, showed a reasonably good match (within 3 kcal/mol) with the experimental values, obtained using “potential pKa” and “hydride-transfer” methods. The hydride donor abilities of model compounds were in the 48.7–85.8 kcal/mol (acetonitrile) and 46.9–84.1 kcal/mol (DMSO) range, making them comparable to previously studied first-row transition metal hydride complexes. To evaluate the relevance of entropic contribution to the overall hydricity, Gibbs free energy differences (ΔGH) obtained in this work were compared with the enthalpy (ΔHH) values obtained by others. The results indicate that, even though ΔHH values exhibit the same trends as ΔGH, the differences between room-temperature ΔGH and ΔHH values range from 3 to 9 kcal/mol. This study also reports a new metal-free hydride donor, namely, an acridine-based compound 3NH, whose hydricity exceeds that of NaBH4. Collectively, this work gives a perspective of use metal-free hydride catalysts in fuel-forming and other reduction processes.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); Petroleum Research Fund (PRF); Ohio Supercomputer Center (OSC); Richard King Mellon Foundation; USDOE
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1467646
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 13; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 56 works
Citation information provided by
Web of Science

References (131)

Large-scale applications of NAD(P)-dependent oxidoreductases: recent developments journal December 1999
Reversible interconversion of carbon dioxide and formate by an electroactive enzyme journal July 2008
Biocatalytic Imine Reduction and Reductive Amination of Ketones journal May 2015
Stereocomplementary Bioreduction of α,β-Unsaturated Dicarboxylic Acids and Dimethyl Esters using Enoate Reductases:  Enzyme- and Substrate-Based Stereocontrol journal December 2007
Asymmetric bioreduction of activated C=C bonds using enoate reductases from the old yellow enzyme family journal April 2007
Enantioselective Brønsted Acid Catalyzed Transfer Hydrogenation:  Organocatalytic Reduction of Imines journal August 2005
Enantioselective Organocatalytic Transfer Hydrogenation Reactions using Hantzsch Esters journal December 2007
Transfer hydrogenation with Hantzsch esters and related organic hydride donors journal January 2012
A Highly Enantioselective Brønsted Acid Catalyzed Cascade Reaction: Organocatalytic Transfer Hydrogenation of Quinolines and their Application in the Synthesis of Alkaloids journal May 2006
Catalytic Asymmetric Transfer Hydrogenation of α-Ketoesters with Hantzsch Esters journal November 2006
A Metal-Free Transfer Hydrogenation: Organocatalytic Conjugate Reduction of ?,?-Unsaturated Aldehydes journal December 2004
Enantioselective Organocatalytic Hydride Reduction journal January 2005
A new homogeneous electrocatalyst for the reduction of carbon dioxide to methanol at low overpotential journal July 1994
Selective Solar-Driven Reduction of CO 2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell journal May 2008
Photochemical and Radiolytic Production of an Organic Hydride Donor with a RuII Complex Containing an NAD+ Model Ligand journal May 2007
Electrochemistry of Acids on Platinum. Application to the Reduction of Carbon Dioxide in the Presence of Pyridinium Ion in Water journal November 2013
Reduction of CO 2 to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine journal November 2014
Catalytic Reduction of CO 2 by Renewable Organohydrides journal December 2015
Electrochemical reactivities of pyridinium in solution: consequences for CO2 reduction mechanisms journal January 2013
Theoretical Insights into Electrochemical CO 2 Reduction Mechanisms Catalyzed by Surface-Bound Nitrogen Heterocycles journal November 2013
Is the Surface Playing a Role during Pyridine-Catalyzed CO 2 Reduction on p-GaP Photoelectrodes? journal August 2016
Electrochemical Reduction of Aqueous Imidazolium on Pt(111) by Proton Coupled Electron Transfer journal November 2014
Comparative Study of Imidazole and Pyridine Catalyzed Reduction of Carbon Dioxide at Illuminated Iron Pyrite Electrodes journal July 2012
A Comparison of Pyridazine and Pyridine as Electrocatalysts for the Reduction of Carbon Dioxide to Methanol journal August 2014
The electrochemical reduction of carbon dioxide (CO2) to methanol in the presence of pyridoxine (vitamin B6) journal March 2016
CO 2 Reduction Catalyzed by Mercaptopteridine on Glassy Carbon journal August 2014
Attempts To Catalyze the Electrochemical CO 2 -to-Methanol Conversion by Biomimetic 2e + 2H + Transferring Molecules journal January 2016
Dihydropteridine/Pteridine as a 2H + /2e Redox Mediator for the Reduction of CO 2 to Methanol: A Computational Study journal April 2017
Electrochemical Reduction of Carbon Dioxide to Methanol in the Presence of Benzannulated Dihydropyridine Additives journal February 2017
Photochemical Properties and Reactivity of a Ru Compound Containing an NAD/NADH-Functionalized 1,10-Phenanthroline Ligand journal February 2016
[Ir(tpy)(bpy)Cl] as a Photocatalyst for CO 2 Reduction under Visible-Light Irradiation journal October 2017
Electrocatalytic Hydrogen Production by an Aluminum(III) Complex: Ligand-Based Proton and Electron Transfer journal August 2015
Ab Initio Calculations of Thermodynamic Hydricities of Transition-Metal Hydrides in Acetonitrile journal August 2007
Development of Molecular Electrocatalysts for Energy Storage journal February 2014
Production of hydrogen by electrocatalysis: making the H–H bond by combining protons and hydrides journal January 2014
Thermodynamic Hydricity of Transition Metal Hydrides journal June 2016
Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium journal February 2016
Aqueous Hydricity from Calculations of Reduction Potential and Acidity in Water journal December 2016
Striking Differences in Properties of Geometric Isomers of [Ir(tpy)(ppy)H] + : Experimental and Computational Studies of their Hydricities, Interaction with CO 2 , and Photochemistry journal October 2015
Solvation Effects on Transition Metal Hydricity journal November 2015
Tailoring Electrocatalysts for Selective CO 2 or H + Reduction: Iron Carbonyl Clusters as a Case Study journal November 2015
Rapid Transfer of Hydride Ion from a Ruthenium Complex to C 1 Species in Water journal August 2007
Bond energies in solution from electrode potentials and thermochemical cycles. A simplified and general approach journal May 1993
Measurement of the Hydride Donor Abilities of [HM(diphosphine) 2 ] + Complexes (M = Ni, Pt) by Heterolytic Activation of Hydrogen journal March 2002
Hydricity of transition-metal hydrides and its role in CO2 reduction journal January 2000
Hydridic character of early transition metal hydride complexes journal August 1978
Periodic Trends in Metal Hydride Donor Thermodynamics:  Measurement and Comparison of the Hydride Donor Abilities of the Series HM(PNP) 2 + (M = Ni, Pd, Pt; PNP = Et 2 PCH 2 N(Me)CH 2 PEt 2 ) journal February 2004
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
Relationship between the bite size of diphosphine ligands and tetrahedral distortions of "square-planar" nickel(II) complexes: stabilization of nickel(I) and palladium(I) complexes using diphosphine ligands with large bites journal February 1991
Using Ligand Bite Angles To Control the Hydricity of Palladium Diphosphine Complexes journal May 2004
Relative Hydride, Proton, and Hydrogen Atom Transfer Abilities of [HM(diphosphine) 2 ]PF 6 Complexes (M = Pt, Ni) journal December 1999
Free-Energy Relationships between the Proton and Hydride Donor Abilities of [HNi(diphosphine) 2 ] + Complexes and the Half-Wave Potentials of Their Conjugate Bases journal April 2001
Thermodynamic Studies of [H 2 Rh(diphosphine) 2 ] + and [HRh(diphosphine) 2 (CH 3 CN)] 2+ Complexes in Acetonitrile journal April 2010
Thermodynamic Hydride Donor Abilities of [HW(CO) 4 L] - Complexes (L = PPh 3 , P(OMe) 3 , CO) and Their Reactions with [C 5 Me 5 Re(PMe 3 )(NO)(CO)] + journal October 2003
Comprehensive Thermochemistry of W–H Bonding in the Metal Hydrides CpW(CO) 2 (IMes)H, [CpW(CO) 2 (IMes)H] •+ , and [CpW(CO) 2 (IMes)(H) 2 ] + . Influence of an N -Heterocyclic Carbene Ligand on Metal Hydride Bond Energies journal September 2011
Hydricities of BzNADH, C 5 H 5 Mo(PMe 3 )(CO) 2 H, and C 5 Me 5 Mo(PMe 3 )(CO) 2 H in Acetonitrile journal March 2004
CO 2 reduction or HCO 2 oxidation? Solvent-dependent thermochemistry of a nickel hydride complex journal January 2017
Hydricities of d 6 Metal Hydride Complexes in Water journal March 2009
Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen journal January 2015
An Iron Electrocatalyst for Selective Reduction of CO 2 to Formate in Water: Including Thermochemical Insights journal November 2015
Solvent influence on the thermodynamics for hydride transfer from bis(diphosphine) complexes of nickel journal January 2016
Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction journal January 2018
Hydride affinities of carbenium ions in acetonitrile and dimethyl sulfoxide solution journal April 1993
Free energy hydride affinities of quinones in dimethyl sulfoxide solution journal September 1993
Hydride Affinities of Organic Cations in Solution. journal January 1992
Theoretical Prediction of the Hydride Affinities of Various p - and o -Quinones in DMSO journal February 2007
Hydride Affinities of Arylcarbenium Ions and Iminium Ions in Dimethyl Sulfoxide and Acetonitrile journal July 1998
Hydride affinities of organic radicals in solution. A comparison of free radicals and carbenium ions as hydride ion acceptors journal June 1993
Hydride, Hydrogen Atom, Proton, and Electron Transfer Driving Forces of Various Five-Membered Heterocyclic Organic Hydrides and Their Reaction Intermediates in Acetonitrile journal February 2008
A Thermodynamic and Kinetic Study of Hydride Transfer of a Caffeine Derivative journal July 2012
Thermodynamic Diagnosis of the Properties and Mechanism of Dihydropyridine-Type Compounds as Hydride Source in Acetonitrile with “Molecule ID Card” journal February 2010
Kinetics of Hydride Abstractions from 2-Arylbenzimidazolines journal October 2009
Hydride-Donor Abilities of 1,4-Dihydropyridines: A Comparison with π Nucleophiles and Borohydride Anions journal March 2009
The Crystal Structure of an [Fe]-Hydrogenase-Substrate Complex Reveals the Framework for H 2 Activation journal August 2009
Systematic optimization of long-range corrected hybrid density functionals journal February 2008
Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections journal January 2008
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model journal March 1998
Toward Organic Photohydrides: Excited-State Behavior of 10-Methyl-9-phenyl-9,10-dihydroacridine journal May 2013
Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide journal January 2007
Toward the accurate calculation of pKa values in water and acetonitrile journal August 2013
Threshold photodetachment of H − journal June 1991
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Effect of the damping function in dispersion corrected density functional theory journal March 2011
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal June 1986
The ORCA program system: The ORCA program system journal June 2011
Absolute Potential of the Standard Hydrogen Electrode and the Problem of Interconversion of Potentials in Different Solvents journal June 2010
Sensitization of p-GaP with Monocationic Dyes: The Effect of Dye Excited-State Lifetime on Hole Injection Efficiencies journal February 2016
Synthesis, Structure, and Properties of Azatriangulenium Salts journal April 2001
Mimicking Nature: Synthetic Nicotinamide Cofactors for C═C Bioreduction Using Enoate Reductases journal December 2012
Excellent correlation between substituent constants and pyridinium N-methyl chemical shifts journal September 2009
Photo-induced reduction of pyridinium ions catalysed by zinc(II) tetraphenylporphyrin journal January 1979
NMR Studies of 2-Aryl Derivatives of Benzimidazole, Benzimidazolium Ion, and Benzimidazoline journal January 2009
Reactions of 8,9-dihydroxanthines with acetylenic compounds. Formation of heteropropellanes. journal January 1985
Carbonium ion-silane hydride transfer reactions. I. Scope and stereochemistry journal May 1968
Highly selective additions of hydride and organolithium nucleophiles to helical carbenium ions journal January 2011
Equilibrium acidities of carbon acids. VI. Establishment of an absolute scale of acidities in dimethyl sulfoxide solution journal November 1975
Energetics of Multistep versus One-step Hydride Transfer Reactions of Reduced Nicotinamide Adenine Dinucleotide (NADH) Models with Organic Cations and p -Quinones journal September 1998
Conversion constants for redox potentials measured versus different reference electrodes in acetonitrile solutions at 25°C journal January 2000
Hydride Dissociation Energies of Six-Membered Heterocyclic Organic Hydrides Predicted by ONIOM-G4Method journal December 2011
Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction journal July 2012
Hydride Donor Abilities of Cationic Transition Metal Hydrides from DFT-PCM Calculations journal January 2006
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO 2 Reduction by fac -Re(bpy)(CO) 3 Cl journal October 2013
Equilibrium acidities in dimethyl sulfoxide solution journal December 1988
Electrochemistry of NADH/NAD+ analogs. A detailed mechanistic kinetic and thermodynamic analysis of the 10-methylacridan/10-methylacridinium couple in acetonitrile journal February 1990
Electrochemistry of synthetic analogues of NAD dimers journal January 1992
Stable free radicals. 12. New aspects of the behavior of 1-alkyl-4-(carboalkoxy)- and 1-alkyl-4-carbamidopyridinyl radicals in solution and in thin films journal August 1981
Electrosynthesis of Imidazolium Carboxylates journal August 2013
Arylethynylacridines: electrochemiluminescence and photophysical properties journal January 2004
Electrochemical reduction of an imidazolium cation: a convenient preparation of imidazol-2-ylidenes and their observation in an ionic liquid journal January 2004
Electrochemical Characterization of Azolium Salts journal June 2014
Electrochemistry of the 9-phenyl-10-methyl-acridan/acridinium redox system; a high-potential NADH/NAD + analogue journal January 1985
Establishing the Hydride Donor Abilities of Main Group Hydrides journal May 2015
Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes journal September 2012
Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs journal January 1988
Formal Transfers of Hydride from Carbon−Hydrogen Bonds. Generation of H 2 from Orthoformamides Designed To Undergo Intramolecular Protonolyses of Activated Carbon−Hydrogen Bonds journal January 1996
The Crystal Structure of [Fe]-Hydrogenase Reveals the Geometry of the Active Site journal July 2008
The coordination chemistry of organo-hydride donors: new prospects for efficient multi-electron reduction journal January 2013
Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation journal December 2009
Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions journal January 2013
Trialkylborane-Assisted CO 2 Reduction by Late Transition Metal Hydrides journal August 2011
Cyclopentadiene-mediated hydride transfer from rhodium complexes journal January 2016
Photoswitchable Hydride Transfer from Iridium to 1-Methylnicotinamide Rationalized by Thermochemical Cycles journal October 2014
Thermodynamic Properties of the Ni−H Bond in Complexes of the Type [HNi(P 2 R N 2 R ) 2 ](BF 4 ) and Evaluation of Factors That Control Catalytic Activity for Hydrogen Oxidation/Production journal July 2007
Mechanistic Insights into Catalytic H 2 Oxidation by Ni Complexes Containing a Diphosphine Ligand with a Positioned Amine Base journal April 2009
Electrocatalytic Oxidation of Formate by [Ni(P R 2 N R′ 2 ) 2 (CH 3 CN)] 2+ Complexes journal August 2011
Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere journal June 2013
Open questions in ferredoxin-NADP+ reductase catalytic mechanism journal May 2003
One-Electron and Two-Electron Transfers in Electrochemistry and Homogeneous Solution Reactions journal July 2008
Electron-transfer reactions and associated conformational changes. Extended redox series for some bianthrones, lucigenin, and dixanthylene journal September 1982

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Figures / Tables (9)