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Title: Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes

Abstract

This Perspective examines the field of Frustrated Lewis Pairs (FLPs) in the context of transition metal mediated heterolytic cleavage of H2, with a particular emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with group compounds, yet many transition metal reactions support a broader classification of FLPs to include certain types of transition metal complexes with reactivity resembling main group based FLPs. This article surveys transition metal complexes that heterolytically cleave H2, which vary in the degree that the Lewis pairs within these systems interact. Particular attention is focused on complexes bearing a pendant amine function as the base. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.

Authors:
ORCiD logo;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Org.:
USDOE
OSTI Identifier:
1378002
Report Number(s):
PNNL-SA-124507
Journal ID: ISSN 1364-503X; KC0307010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences
Additional Journal Information:
Journal Volume: 375; Journal Issue: 2101; Journal ID: ISSN 1364-503X
Publisher:
The Royal Society Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterolytic; hydrogen; cleavage; frustrated; hydride; proton; hydrogenase

Citation Formats

Bullock, R. Morris, and Chambers, Geoffrey M. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes. United States: N. p., 2017. Web. doi:10.1098/rsta.2017.0002.
Bullock, R. Morris, & Chambers, Geoffrey M. Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes. United States. doi:10.1098/rsta.2017.0002.
Bullock, R. Morris, and Chambers, Geoffrey M. Mon . "Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes". United States. doi:10.1098/rsta.2017.0002.
@article{osti_1378002,
title = {Frustration across the periodic table: heterolytic cleavage of dihydrogen by metal complexes},
author = {Bullock, R. Morris and Chambers, Geoffrey M.},
abstractNote = {This Perspective examines the field of Frustrated Lewis Pairs (FLPs) in the context of transition metal mediated heterolytic cleavage of H2, with a particular emphasis on molecular complexes bearing an intramolecular Lewis base. FLPs have traditionally been associated with group compounds, yet many transition metal reactions support a broader classification of FLPs to include certain types of transition metal complexes with reactivity resembling main group based FLPs. This article surveys transition metal complexes that heterolytically cleave H2, which vary in the degree that the Lewis pairs within these systems interact. Particular attention is focused on complexes bearing a pendant amine function as the base. Consideration of transition metal compounds in the context of FLPs can inspire new innovations and improvements in transition metal catalysis.},
doi = {10.1098/rsta.2017.0002},
journal = {Philosophical Transactions of the Royal Society. A, Mathematical, Physical and Engineering Sciences},
issn = {1364-503X},
number = 2101,
volume = 375,
place = {United States},
year = {2017},
month = {7}
}

Works referenced in this record:

Modular Attachment of Appended Boron Lewis Acids to a Ruthenium Pincer Catalyst: Metal–Ligand Cooperativity Enables Selective Alkyne Hydrogenation
journal, August 2016

  • Tseng, Kuei-Nin T.; Kampf, Jeff W.; Szymczak, Nathaniel K.
  • Journal of the American Chemical Society, Vol. 138, Issue 33
  • DOI: 10.1021/jacs.6b03972

Practical Enantioselective Hydrogenation of Aromatic Ketones
journal, March 1995

  • Ohkuma, Takeshi; Ooka, Hirohito; Hashiguchi, Shohei
  • Journal of the American Chemical Society, Vol. 117, Issue 9
  • DOI: 10.1021/ja00114a043

Reversible, Metal-Free Hydrogen Activation
journal, November 2006


Reversible H 2 Addition across a Nickel–Borane Unit as a Promising Strategy for Catalysis
journal, March 2012

  • Harman, W. Hill; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 134, Issue 11
  • DOI: 10.1021/ja211419t

Synthesis, Structure, and Reactivity of Monomeric Titanocene Sulfido and Disulfide Complexes. Reaction of H 2 with a Terminal MS Bond
journal, May 1997

  • Sweeney, Zachary K.; Polse, Jennifer L.; Andersen, Richard A.
  • Journal of the American Chemical Society, Vol. 119, Issue 19
  • DOI: 10.1021/ja970168t

Importance of the Active Site “Canopy” Residues in an O 2 -Tolerant [NiFe]-Hydrogenase
journal, December 2016


Metal-Ligand Cooperation
journal, September 2015

  • Khusnutdinova, Julia R.; Milstein, David
  • Angewandte Chemie International Edition, Vol. 54, Issue 42
  • DOI: 10.1002/anie.201503873

Hydrogen-activating models of hydrogenases
journal, November 2015


Hydrogen atom storage upon Z-class borane ligand functions: an alternative approach to ligand cooperation
journal, January 2012


[Ni(P Ph 2 N C6H4X 2 ) 2 ] 2+ Complexes as Electrocatalysts for H 2 Production: Effect of Substituents, Acids, and Water on Catalytic Rates
journal, April 2011

  • Kilgore, Uriah J.; Roberts, John A. S.; Pool, Douglas H.
  • Journal of the American Chemical Society, Vol. 133, Issue 15
  • DOI: 10.1021/ja109755f

Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H⋅⋅⋅H-N Dihydrogen Bond Characterized by Neutron Diffraction
journal, April 2014

  • Liu, Tianbiao; Wang, Xiaoping; Hoffmann, Christina
  • Angewandte Chemie International Edition, Vol. 53, Issue 21
  • DOI: 10.1002/anie.201402090

A Significant but Constrained Geometry Pt→Al Interaction: Fixation of CO 2 and CS 2 , Activation of H 2 and PhCONH 2
journal, March 2016

  • Devillard, Marc; Declercq, Richard; Nicolas, Emmanuel
  • Journal of the American Chemical Society, Vol. 138, Issue 14
  • DOI: 10.1021/jacs.6b01320

Iron-Chromophore Circular Dichroism of [Fe]-Hydrogenase: The Conformational Change Required for H2 Activation
journal, November 2010

  • Shima, Seigo; Vogt, Sonja; Göbels, Andreas
  • Angewandte Chemie International Edition, Vol. 49, Issue 51
  • DOI: 10.1002/anie.201006255

Structure of the [NiFe] Hydrogenase Active Site:  Evidence for Biologically Uncommon Fe Ligands
journal, January 1996

  • Volbeda, Anne; Garcin, Elsa; Piras, Claudine
  • Journal of the American Chemical Society, Vol. 118, Issue 51
  • DOI: 10.1021/ja962270g

Cooperative Transition Metal/Lewis Acid Bond-Activation Reactions by a Bidentate (Boryl)iminomethane Complex: A Significant Metal–Borane Interaction Promoted by a Small Bite-Angle LZ Chelate
journal, July 2014

  • Barnett, Brandon R.; Moore, Curtis E.; Rheingold, Arnold L.
  • Journal of the American Chemical Society, Vol. 136, Issue 29
  • DOI: 10.1021/ja505843g

Heterolytic Activation of Dihydrogen Molecule by Hydroxo-/Sulfido-Bridged Ruthenium–Germanium Dinuclear Complex. Theoretical Insights
journal, December 2014

  • Ochi, Noriaki; Matsumoto, Tsuyoshi; Dei, Takeya
  • Inorganic Chemistry, Vol. 54, Issue 2
  • DOI: 10.1021/ic502463y

Bond energies in solution from electrode potentials and thermochemical cycles. A simplified and general approach
journal, May 1993

  • Wayner, Danial D. M.; Parker, Vernon D.
  • Accounts of Chemical Research, Vol. 26, Issue 5
  • DOI: 10.1021/ar00029a010

Dihydrogen Bonding:  Structures, Energetics, and Dynamics
journal, July 2001

  • Custelcean, Radu; Jackson, James E.
  • Chemical Reviews, Vol. 101, Issue 7
  • DOI: 10.1021/cr000021b

Heterolytic Cleavage of Hydrogen Molecule by Rhodium Thiolate Complexes That Catalyze Chemoselective Hydrogenation of Imines under Ambient Conditions
journal, October 2009

  • Misumi, Yoshiyuki; Seino, Hidetake; Mizobe, Yasushi
  • Journal of the American Chemical Society, Vol. 131, Issue 41
  • DOI: 10.1021/ja905835u

Cooperating Ligands in Catalysis
journal, February 2008

  • Grützmacher, Hansjörg
  • Angewandte Chemie International Edition, Vol. 47, Issue 10
  • DOI: 10.1002/anie.200704654

Dihydrogen Activation by Titanium Sulfide Complexes
journal, December 1999

  • Sweeney, Zachary K.; Polse, Jennifer L.; Bergman, Robert G.
  • Organometallics, Vol. 18, Issue 26
  • DOI: 10.1021/om9907876

Reversible Heterolysis of H 2 Mediated by an M−S(Thiolate) Bond (M = Ir, Rh): A Mechanistic Implication for [NiFe] Hydrogenase
journal, September 2008

  • Ohki, Yasuhiro; Sakamoto, Mayumi; Tatsumi, Kazuyuki
  • Journal of the American Chemical Society, Vol. 130, Issue 35
  • DOI: 10.1021/ja804848w

Heterolytic Dihydrogen Activation by a Sulfido- and Oxo-Bridged Dinuclear Germanium–Ruthenium Complex
journal, February 2008

  • Matsumoto, Tsuyoshi; Nakaya, Yukiko; Tatsumi, Kazuyuki
  • Angewandte Chemie International Edition, Vol. 47, Issue 10
  • DOI: 10.1002/anie.200704899

Iron Complexes Bearing Diphosphine Ligands with Positioned Pendant Amines as Electrocatalysts for the Oxidation of H 2
journal, May 2015

  • Liu, Tianbiao; Liao, Qian; O’Hagan, Molly
  • Organometallics, Vol. 34, Issue 12
  • DOI: 10.1021/om501289f

Enzymes as Working or Inspirational Electrocatalysts for Fuel Cells and Electrolysis
journal, July 2008

  • Cracknell, James A.; Vincent, Kylie A.; Armstrong, Fraser A.
  • Chemical Reviews, Vol. 108, Issue 7
  • DOI: 10.1021/cr0680639

The mechanism of enantioselective ketone reduction with Noyori and Noyori–Ikariya bifunctional catalysts
journal, January 2016

  • Dub, Pavel A.; Gordon, John C.
  • Dalton Transactions, Vol. 45, Issue 16
  • DOI: 10.1039/C6DT00476H

A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration
journal, September 2015

  • Geri, Jacob B.; Szymczak, Nathaniel K.
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b08406

Double addition of H 2 to transition metal–borane complexes: a ‘hydride shuttle’ process between boron and transition metal centres
journal, January 2011

  • Tsoureas, Nikolaos; Kuo, Yu-Ying; Haddow, Mairi F.
  • Chem. Commun., Vol. 47, Issue 1
  • DOI: 10.1039/C0CC02245D

Amine(imine)diphosphine Iron Catalysts for Asymmetric Transfer Hydrogenation of Ketones and Imines
journal, November 2013


Hydrogen Activation by Frustrated Lewis Pairs Revisited by Metadynamics Simulations
journal, January 2017

  • Liu, Lei; Lukose, Binit; Ensing, Bernd
  • The Journal of Physical Chemistry C, Vol. 121, Issue 4
  • DOI: 10.1021/acs.jpcc.6b09991

Combining acid–base, redox and substrate binding functionalities to give a complete model for the [FeFe]-hydrogenase
journal, October 2011

  • Camara, James M.; Rauchfuss, Thomas B.
  • Nature Chemistry, Vol. 4, Issue 1
  • DOI: 10.1038/nchem.1180

Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen
journal, November 2015


Electronic Control of Frustrated Lewis Pair Behavior: Chemistry of a Geminal Alkylidene-Bridged Per-pentafluorophenylated P/B Pair
journal, August 2011

  • Rosorius, Christoph; Kehr, Gerald; Fröhlich, Roland
  • Organometallics, Vol. 30, Issue 15
  • DOI: 10.1021/om200569k

A Functional [NiFe]Hydrogenase Mimic That Catalyzes Electron and Hydride Transfer from H2
journal, February 2013


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

  • Hou, Jianbo; Fang, Ming; Cardenas, Allan Jay P.
  • Energy Environ. Sci., Vol. 7, Issue 12
  • DOI: 10.1039/C4EE01899K

An iron complex with pendent amines as a molecular electrocatalyst for oxidation of hydrogen
journal, February 2013

  • Liu, Tianbiao; DuBois, Daniel L.; Bullock, R. Morris
  • Nature Chemistry, Vol. 5, Issue 3
  • DOI: 10.1038/nchem.1571

Manganese-Based Molecular Electrocatalysts for Oxidation of Hydrogen
journal, October 2015


Unravelling the Mechanism of the Asymmetric Hydrogenation of Acetophenone by [RuX 2 (diphosphine)(1,2-diamine)] Catalysts
journal, February 2014

  • Dub, Pavel A.; Henson, Neil J.; Martin, Richard L.
  • Journal of the American Chemical Society, Vol. 136, Issue 9
  • DOI: 10.1021/ja411374j

Rapid, Reversible Heterolytic Cleavage of Bound H 2
journal, July 2013

  • Hulley, Elliott B.; Welch, Kevin D.; Appel, Aaron M.
  • Journal of the American Chemical Society, Vol. 135, Issue 32
  • DOI: 10.1021/ja405755j

Gold-Catalyzed Organic Reactions
journal, July 2007


Crystal structure of the nickel–iron hydrogenase from Desulfovibrio gigas
journal, February 1995

  • Volbeda, Anne; Charon, Marie-Hélène; Piras, Claudine
  • Nature, Vol. 373, Issue 6515
  • DOI: 10.1038/373580a0

Mechanistic Insights into Catalytic H 2 Oxidation by Ni Complexes Containing a Diphosphine Ligand with a Positioned Amine Base
journal, April 2009

  • Yang, Jenny Y.; Bullock, R. Morris; Shaw, Wendy J.
  • Journal of the American Chemical Society, Vol. 131, Issue 16
  • DOI: 10.1021/ja900483x

Structure/Function Relationships of [NiFe]- and [FeFe]-Hydrogenases
journal, October 2007

  • Fontecilla-Camps, Juan C.; Volbeda, Anne; Cavazza, Christine
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr050195z

Coordination chemistry of dihydrogen
journal, May 1993

  • Heinekey, D. M.; Oldham, Warren J.
  • Chemical Reviews, Vol. 93, Issue 3
  • DOI: 10.1021/cr00019a004

Synthesis, Structures, and Reactions of Manganese Complexes Containing Diphosphine Ligands with Pendant Amines
journal, October 2010

  • Welch, Kevin D.; Dougherty, William G.; Kassel, W. Scott
  • Organometallics, Vol. 29, Issue 20
  • DOI: 10.1021/om100668e

Homogeneous Catalysis with Inexpensive Metals:  Ionic Hydrogenation of Ketones with Molybdenum and Tungsten Catalysts
journal, December 2000

  • Bullock, R. Morris; Voges, Mark H.
  • Journal of the American Chemical Society, Vol. 122, Issue 50
  • DOI: 10.1021/ja0010599

Heterolytic Cleavage of Dihydrogen Promoted by Sulfido-Bridged Tungsten−Ruthenium Dinuclear Complexes
journal, July 2003

  • Ohki, Yasuhiro; Matsuura, Nobuo; Marumoto, Tadashi
  • Journal of the American Chemical Society, Vol. 125, Issue 26
  • DOI: 10.1021/ja029941x

Predicting the reactivity of hydride donors in water: thermodynamic constants for hydrogen
journal, January 2015

  • Connelly, Samantha J.; Wiedner, Eric S.; Appel, Aaron M.
  • Dalton Transactions, Vol. 44, Issue 13
  • DOI: 10.1039/C4DT03841J

Catalytic Activation of H 2 under Mild Conditions by an [FeFe]-Hydrogenase Model via an Active μ-Hydride Species
journal, September 2013

  • Wang, Ning; Wang, Mei; Wang, Ying
  • Journal of the American Chemical Society, Vol. 135, Issue 37
  • DOI: 10.1021/ja408376t

Nickel Bis-Diphosphine Complexes: Controlling the Binding and Heterolysis of H 2
journal, August 2016


Hydrogenases
journal, March 2014

  • Lubitz, Wolfgang; Ogata, Hideaki; Rüdiger, Olaf
  • Chemical Reviews, Vol. 114, Issue 8
  • DOI: 10.1021/cr4005814

The Role of Pendant Amines in the Breaking and Forming of Molecular Hydrogen Catalyzed by Nickel Complexes
journal, April 2012

  • Raugei, Simone; Chen, Shentan; Ho, Ming-Hsun
  • Chemistry - A European Journal, Vol. 18, Issue 21
  • DOI: 10.1002/chem.201103346

Quantum Chemical Calculations with the Inclusion of Nonspecific and Specific Solvation: Asymmetric Transfer Hydrogenation with Bifunctional Ruthenium Catalysts
journal, February 2013

  • Dub, Pavel A.; Ikariya, Takao
  • Journal of the American Chemical Society, Vol. 135, Issue 7
  • DOI: 10.1021/ja3097674

Metal–Ligand Cooperation by Aromatization–Dearomatization: A New Paradigm in Bond Activation and “Green” Catalysis
journal, August 2011

  • Gunanathan, Chidambaram; Milstein, David
  • Accounts of Chemical Research, Vol. 44, Issue 8
  • DOI: 10.1021/ar2000265

A Dinuclear Ni( -H)Ru Complex Derived from H2
journal, April 2007


Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 p K a Units:  Unification of Different Basicity Scales
journal, February 2005

  • Kaljurand, Ivari; Kütt, Agnes; Sooväli, Lilli
  • The Journal of Organic Chemistry, Vol. 70, Issue 3
  • DOI: 10.1021/jo048252w

Heterolytic H 2 Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane
journal, May 2013

  • Fong, Henry; Moret, Marc-Etienne; Lee, Yunho
  • Organometallics, Vol. 32, Issue 10
  • DOI: 10.1021/om400281v

Reactivity Models of Hydrogen Activation by Frustrated Lewis Pairs: Synergistic Electron Transfers or Polarization by Electric Field?
journal, March 2013

  • Rokob, Tibor András; Bakó, Imre; Stirling, András
  • Journal of the American Chemical Society, Vol. 135, Issue 11
  • DOI: 10.1021/ja312387q

Electronic control in frustrated Lewis pair chemistry: adduct formation of intramolecular FLP systems with –P(C6F5)2 Lewis base components
journal, January 2013

  • Stute, Annika; Kehr, Gerald; Daniliuc, Constantin G.
  • Dalton Transactions, Vol. 42, Issue 13
  • DOI: 10.1039/c2dt32806b

Catalytic Ionic Hydrogenations
journal, May 2004


Functional Model for the [Fe] Hydrogenase Inspired by the Frustrated Lewis Pair Concept
journal, November 2014

  • Kalz, Kai F.; Brinkmeier, Alexander; Dechert, Sebastian
  • Journal of the American Chemical Society, Vol. 136, Issue 47
  • DOI: 10.1021/ja509186d

Metal−Ligand Bifunctional Catalysis:  A Nonclassical Mechanism for Asymmetric Hydrogen Transfer between Alcohols and Carbonyl Compounds
journal, November 2001

  • Noyori, Ryoji; Yamakawa, Masashi; Hashiguchi, Shohei
  • The Journal of Organic Chemistry, Vol. 66, Issue 24
  • DOI: 10.1021/jo010721w

Transition Metal Frustrated Lewis Pairs
journal, October 2013

  • Flynn, Stephanie R.; Wass, Duncan F.
  • ACS Catalysis, Vol. 3, Issue 11
  • DOI: 10.1021/cs400754w

Frustrated Lewis Pair vs Metal–Carbon σ-Bond Insertion Chemistry at an o -Phenylene-Bridged Cp 2 Zr + /PPh 2 System
journal, January 2017


How Formaldehyde Inhibits Hydrogen Evolution by [FeFe]-Hydrogenases: Determination by 13 C ENDOR of Direct Fe–C Coordination and Order of Electron and Proton Transfers
journal, April 2015

  • Bachmeier, Andreas; Esselborn, Julian; Hexter, Suzannah V.
  • Journal of the American Chemical Society, Vol. 137, Issue 16
  • DOI: 10.1021/ja513074m

[Ni(Et 2 PCH 2 NMeCH 2 PEt 2 ) 2 ] 2+ as a Functional Model for Hydrogenases
journal, January 2003

  • Curtis, Calvin J.; Miedaner, Alex; Ciancanelli, Rebecca
  • Inorganic Chemistry, Vol. 42, Issue 1
  • DOI: 10.1021/ic020610v

Thermodynamic Hydricity of Transition Metal Hydrides
journal, June 2016


Iron Complexes for the Electrocatalytic Oxidation of Hydrogen: Tuning Primary and Secondary Coordination Spheres
journal, March 2014

  • Darmon, Jonathan M.; Raugei, Simone; Liu, Tianbiao
  • ACS Catalysis, Vol. 4, Issue 4
  • DOI: 10.1021/cs500290w

Controlling Proton Delivery through Catalyst Structural Dynamics
journal, September 2016

  • Cardenas, Allan Jay P.; Ginovska, Bojana; Kumar, Neeraj
  • Angewandte Chemie International Edition, Vol. 55, Issue 43
  • DOI: 10.1002/anie.201607460

Unconventional Hydrogen Bonds: Intermolecular B-H.cntdot..cntdot..cntdot.H-N Interactions
journal, December 1995

  • Richardson, Thomas; de Gala, Susan; Crabtree, Robert H.
  • Journal of the American Chemical Society, Vol. 117, Issue 51
  • DOI: 10.1021/ja00156a032

Gold-Catalyzed Organic Transformations
journal, August 2008

  • Li, Zigang; Brouwer, Chad; He, Chuan
  • Chemical Reviews, Vol. 108, Issue 8
  • DOI: 10.1021/cr068434l

Reversible Heterolytic Cleavage of the H–H Bond by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and Hydride
journal, May 2017

  • Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris
  • Journal of the American Chemical Society, Vol. 139, Issue 21
  • DOI: 10.1021/jacs.7b03053

A New Intermolecular Interaction:  UnconventionalHydrogen Bonds with Element−Hydride Bonds as ProtonAcceptor
journal, January 1996

  • Crabtree, Robert H.; Siegbahn, Per E. M.; Eisenstein, Odile
  • Accounts of Chemical Research, Vol. 29, Issue 7
  • DOI: 10.1021/ar950150s

Dihydrogen Complexation
journal, March 2016


The Mechanism of Dihydrogen Activation by Frustrated Lewis Pairs Revisited
journal, January 2010

  • Grimme, Stefan; Kruse, Holger; Goerigk, Lars
  • Angewandte Chemie International Edition, Vol. 49, Issue 8
  • DOI: 10.1002/anie.200905484

Ketone Hydrogenation with Iridium Complexes with “non N–H” Ligands: The Key Role of the Strong Base
journal, June 2015


Heterolytic dihydrogen activation in an iridium complex with a pendant basic group
journal, January 1999

  • Lee, Dong-Heon; Patel, Ben P.; Crabtree, Robert H.
  • Chemical Communications, Issue 3
  • DOI: 10.1039/a808601j

Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes
journal, July 1995

  • Hashiguchi, Shohei; Fujii, Akio; Takehara, Jun
  • Journal of the American Chemical Society, Vol. 117, Issue 28
  • DOI: 10.1021/ja00133a037

Heterolytic cleavage of H 2 by bifunctional manganese( i ) complexes: impact of ligand dynamics, electrophilicity, and base positioning
journal, January 2014

  • Hulley, Elliott B.; Helm, Monte L.; Bullock, R. Morris
  • Chem. Sci., Vol. 5, Issue 12
  • DOI: 10.1039/C4SC01801J

Frustrated Lewis Pairs beyond the Main Group: Synthesis, Reactivity, and Small Molecule Activation with Cationic Zirconocene–Phosphinoaryloxide Complexes
journal, November 2011

  • Chapman, Andy M.; Haddow, Mairi F.; Wass, Duncan F.
  • Journal of the American Chemical Society, Vol. 133, Issue 45
  • DOI: 10.1021/ja207936p

A Functional Model of [Fe]-Hydrogenase
journal, March 2016

  • Xu, Tao; Yin, Chih-Juo Madeline; Wodrich, Matthew D.
  • Journal of the American Chemical Society, Vol. 138, Issue 10
  • DOI: 10.1021/jacs.5b12095

Dihydrogen and Acetylene Activation by a Gold(I)/Platinum(0) Transition Metal Only Frustrated Lewis Pair
journal, February 2017

  • Campos, Jesús
  • Journal of the American Chemical Society, Vol. 139, Issue 8
  • DOI: 10.1021/jacs.7b00491

Why Does Alkylation of the N–H Functionality within M/NH Bifunctional Noyori-Type Catalysts Lead to Turnover?
journal, January 2017

  • Dub, Pavel A.; Scott, Brian L.; Gordon, John C.
  • Journal of the American Chemical Society, Vol. 139, Issue 3
  • DOI: 10.1021/jacs.6b11666

Conformational Dynamics and Proton Relay Positioning in Nickel Catalysts for Hydrogen Production and Oxidation
journal, November 2013

  • Franz, James A.; O’Hagan, Molly; Ho, Ming-Hsun
  • Organometallics, Vol. 32, Issue 23
  • DOI: 10.1021/om400695w

Brønsted–Lowry Acid Strength of Metal Hydride and Dihydrogen Complexes
journal, March 2016


Mild Redox Complementation Enables H 2 Activation by [FeFe]-Hydrogenase Models
journal, June 2011

  • Camara, James M.; Rauchfuss, Thomas B.
  • Journal of the American Chemical Society, Vol. 133, Issue 21
  • DOI: 10.1021/ja201731q

Exploiting Metal–Ligand Bifunctional Reactions in the Design of Iron Asymmetric Hydrogenation Catalysts
journal, April 2015


Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere
journal, June 2013

  • Yang, Jenny Y.; Smith, Stuart E.; Liu, Tianbiao
  • Journal of the American Chemical Society, Vol. 135, Issue 26
  • DOI: 10.1021/ja400705a

Combinations of Ethers and B(C 6 F 5 ) 3 Function as Hydrogenation Catalysts
journal, June 2013

  • Hounjet, Lindsay J.; Bannwarth, Christoph; Garon, Christian N.
  • Angewandte Chemie International Edition, Vol. 52, Issue 29
  • DOI: 10.1002/anie.201303166

Hydrogen Oxidation and Production Using Nickel-Based Molecular Catalysts with Positioned Proton Relays
journal, January 2006

  • Wilson, Aaron D.; Newell, Rachel H.; McNevin, Michael J.
  • Journal of the American Chemical Society, Vol. 128, Issue 1
  • DOI: 10.1021/ja056442y

Production of hydrogen by electrocatalysis: making the H–H bond by combining protons and hydrides
journal, January 2014

  • Bullock, R. Morris; Appel, Aaron M.; Helm, Monte L.
  • Chem. Commun., Vol. 50, Issue 24
  • DOI: 10.1039/C3CC46135A

Cationic Manganese(I) Dihydrogen and Dinitrogen Complexes Derived from a Formally 16-Electron Complex with a Bis-Agostic Interaction, [Mn(CO)(Ph 2 PC 2 H 4 PPh 2 ) 2 ] +
journal, January 1996

  • King, Wayne A.; Luo, Xiao-Liang; Scott, Brian L.
  • Journal of the American Chemical Society, Vol. 118, Issue 28
  • DOI: 10.1021/ja960499q

Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile Covering the Range between Pyridine and DBU
journal, September 2000

  • Kaljurand, Ivari; Rodima, Toomas; Leito, Ivo
  • The Journal of Organic Chemistry, Vol. 65, Issue 19
  • DOI: 10.1021/jo005521j

Investigating and Exploiting the Electrocatalytic Properties of Hydrogenases
journal, October 2007

  • Vincent, Kylie A.; Parkin, Alison; Armstrong, Fraser A.
  • Chemical Reviews, Vol. 107, Issue 10, p. 4366-4413
  • DOI: 10.1021/cr050191u

Synthesis, Characterization, and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H 2
journal, March 2012

  • Liu, Tianbiao; Chen, Shentan; O’Hagan, Molly J.
  • Journal of the American Chemical Society, Vol. 134, Issue 14
  • DOI: 10.1021/ja211193j

Hydrogen Activation by Biomimetic [NiFe]-Hydrogenase Model Containing Protected Cyanide Cofactors
journal, July 2013

  • Manor, Brian C.; Rauchfuss, Thomas B.
  • Journal of the American Chemical Society, Vol. 135, Issue 32
  • DOI: 10.1021/ja404580r

Synthetic Models for the Active Site of the [FeFe]-Hydrogenase: Catalytic Proton Reduction and the Structure of the Doubly Protonated Intermediate
journal, November 2012

  • Carroll, Maria E.; Barton, Bryan E.; Rauchfuss, Thomas B.
  • Journal of the American Chemical Society, Vol. 134, Issue 45
  • DOI: 10.1021/ja309216v