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67. Zhang S, Appel AM, Bullock RM (2017) Reversible Heterolytic Cleavage of the H−H Bond
by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and
Hydride. J Am Chem Soc 139:7376–7387. https://doi.org/10.1021/jacs.7b03053
68. Hulley EB, Welch KD, Appel AM, DuBois DL, Bullock RM (2013) Rapid, Reversible
Heterolytic Cleavage of Bound H 2 . J Am Chem Soc 135:11736–11739. https://doi.org/10.
1021/ja405755j
69. Hulley EB, Helm ML, Bullock RM (2014) Heterolytic Cleavage of H 2 by Bifunctional Manganese (I) Complexes: Impact of Ligand Dynamics, Electrophilicity, and Base
Positioning. Chem Sci 5:4729–4741. https://doi.org/10.1039/c4sc01801j
70. Liu T, DuBois DL, Bullock RM (2013) An Iron Complex with Pendent Amines as a Molecular
Electrocatalyst for Oxidation of Hydrogen. Nat Chem 5:228–233. https://doi.org/10.1038/
nchem.1571
71. Liu T, Wang X, Hoffmann C, DuBois DL, Bullock RM (2014) Heterolytic Cleavage of
Hydrogen by an Iron Hydrogenase Model: An Fe-H···H-N Dihydrogen Bond Characterized
by Neutron Diffraction. Angew Chem Int Ed 53:5300–5304. https://doi.org/10.1002/anie.201
402090
72. Liu T, Liao Q, Hagan MO, Hulley EB, DuBois DL, Bullock RM (2015) Iron Complexes
Bearing Diphosphine Ligands with Positioned Pendant Amines as Electrocatalysts for the
Oxidation of H 2 . Organometallics 34:2747–2764. https://doi.org/10.1021/om501289f
73. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/Function Relationships of [NiFe]- and [FeFe]-Hydrogenases. Chem Rev 107:4273–4303. https://doi.org/10.
1021/cr050195z
74. Lubitz W, Ogata H, Rüdiger O, Reijerse E (2014) Hydrogenases. Chem Rev 114:4081–4148.
https://doi.org/10.1021/cr4005814
75. Zhang S, Bullock RM (2015) Molybdenum Hydride and Dihydride Complexes Bearing
Diphosphine Ligands with a Pendant Amine: Formation of Complexes with Bound Amines.
Inorg Chem 54:6397–6409. https://doi.org/10.1021/acs.inorgchem.5b00728
76. Melen RL (2018) A Step Closer to Metal-Free Dinitrogen Activation: A New Chapter in the
Chemistry of Frustrated Lewis Pairs. Angew Chem Int Ed 57:880–882. https://doi.org/10.
1002/anie.201711945
77. Tang C, Liang Q, Jupp AR, Johnstone TC, Neu RC, Song D, Grimme S, Stephan DW (2017)
1,1-Hydroboration and a Borane Adduct of Diphenyldiazomethane: A Potential Prelude to
FLP-N 2 Chemistry. Angew Chem Int Ed 56:16588–16592. https://doi.org/10.1002/anie.201
710337
78. Geri JB, Shanahan JP, Szymczak NK (2017) Testing the Push−Pull Hypothesis: Lewis Acid
Augmented N 2 Activation at Iron. J Am Chem Soc 139:5952–5956. https://doi.org/10.1021/
jacs.7b01982
79. Simonneau A, Turrel R, Vendier L, Etienne M (2017) Group 6 Transition-Metal/Boron Frustrated Lewis Pair Templates Activate N 2 and Allow its Facile Borylation and Silylation. Angew
Chem Int Ed 56:12268–12272. https://doi.org/10.1002/anie.201706226
80. Rokob TA, Pápai I (2013) Hydrogen Activation by Frustrated Lewis Pairs: Insights From
Computational Studies. In: Erker G, Stephan D (eds) Frustrated Lewis Pairs I. Topics in
Current Chemistry. Springer, Berlin, Heidelberg, p 157–212. https://doi.org/10.1007/128_
2012_399
81. Paradies J (2019) Mechanisms in Frustrated Lewis Pair-Catalyzed Reactions. Eur J Org Chem
283−294. https://doi.org/10.1002/ejoc.201800944
82. Rocchigiani L (2015) Experimental Insights into the Structure and Reactivity of Frustrated
Lewis Pairs. Isr J Chem 55:134–149. https://doi.org/10.1002/ijch.201400139
83. Liu L, Lukose B, Jaque P, Ensing B (2019) Reaction Mechanism of Hydrogen Activation by
Frustrated Lewis Pairs. Green Energy Environ 4:20–28. https://doi.org/10.1016/j.gee.2018.
06.001
84. Hoffman BM, Lukoyanov D, Yang Z-Y, Dean DR, Seefeldt LC (2014) Mechanism of Nitrogen
Fixation by Nitrogenase: The Next Stage. Chem Rev 114:4041–4062. https://doi.org/10.1021/
cr400641x
N. Hidalgo et al.
67. Zhang S, Appel AM, Bullock RM (2017) Reversible Heterolytic Cleavage of the H−H Bond
by Molybdenum Complexes: Controlling the Dynamics of Exchange Between Proton and
Hydride. J Am Chem Soc 139:7376–7387. https://doi.org/10.1021/jacs.7b03053
68. Hulley EB, Welch KD, Appel AM, DuBois DL, Bullock RM (2013) Rapid, Reversible
Heterolytic Cleavage of Bound H 2 . J Am Chem Soc 135:11736–11739. https://doi.org/10.
1021/ja405755j
69. Hulley EB, Helm ML, Bullock RM (2014) Heterolytic Cleavage of H 2 by Bifunctional Manganese (I) Complexes: Impact of Ligand Dynamics, Electrophilicity, and Base
Positioning. Chem Sci 5:4729–4741. https://doi.org/10.1039/c4sc01801j
70. Liu T, DuBois DL, Bullock RM (2013) An Iron Complex with Pendent Amines as a Molecular
Electrocatalyst for Oxidation of Hydrogen. Nat Chem 5:228–233. https://doi.org/10.1038/
nchem.1571
71. Liu T, Wang X, Hoffmann C, DuBois DL, Bullock RM (2014) Heterolytic Cleavage of
Hydrogen by an Iron Hydrogenase Model: An Fe-H···H-N Dihydrogen Bond Characterized
by Neutron Diffraction. Angew Chem Int Ed 53:5300–5304. https://doi.org/10.1002/anie.201
402090
72. Liu T, Liao Q, Hagan MO, Hulley EB, DuBois DL, Bullock RM (2015) Iron Complexes
Bearing Diphosphine Ligands with Positioned Pendant Amines as Electrocatalysts for the
Oxidation of H 2 . Organometallics 34:2747–2764. https://doi.org/10.1021/om501289f
73. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/Function Relationships of [NiFe]- and [FeFe]-Hydrogenases. Chem Rev 107:4273–4303. https://doi.org/10.
1021/cr050195z
74. Lubitz W, Ogata H, Rüdiger O, Reijerse E (2014) Hydrogenases. Chem Rev 114:4081–4148.
https://doi.org/10.1021/cr4005814
75. Zhang S, Bullock RM (2015) Molybdenum Hydride and Dihydride Complexes Bearing
Diphosphine Ligands with a Pendant Amine: Formation of Complexes with Bound Amines.
Inorg Chem 54:6397–6409. https://doi.org/10.1021/acs.inorgchem.5b00728
76. Melen RL (2018) A Step Closer to Metal-Free Dinitrogen Activation: A New Chapter in the
Chemistry of Frustrated Lewis Pairs. Angew Chem Int Ed 57:880–882. https://doi.org/10.
1002/anie.201711945
77. Tang C, Liang Q, Jupp AR, Johnstone TC, Neu RC, Song D, Grimme S, Stephan DW (2017)
1,1-Hydroboration and a Borane Adduct of Diphenyldiazomethane: A Potential Prelude to
FLP-N 2 Chemistry. Angew Chem Int Ed 56:16588–16592. https://doi.org/10.1002/anie.201
710337
78. Geri JB, Shanahan JP, Szymczak NK (2017) Testing the Push−Pull Hypothesis: Lewis Acid
Augmented N 2 Activation at Iron. J Am Chem Soc 139:5952–5956. https://doi.org/10.1021/
jacs.7b01982
79. Simonneau A, Turrel R, Vendier L, Etienne M (2017) Group 6 Transition-Metal/Boron Frustrated Lewis Pair Templates Activate N 2 and Allow its Facile Borylation and Silylation. Angew
Chem Int Ed 56:12268–12272. https://doi.org/10.1002/anie.201706226
80. Rokob TA, Pápai I (2013) Hydrogen Activation by Frustrated Lewis Pairs: Insights From
Computational Studies. In: Erker G, Stephan D (eds) Frustrated Lewis Pairs I. Topics in
Current Chemistry. Springer, Berlin, Heidelberg, p 157–212. https://doi.org/10.1007/128_
2012_399
81. Paradies J (2019) Mechanisms in Frustrated Lewis Pair-Catalyzed Reactions. Eur J Org Chem
283−294. https://doi.org/10.1002/ejoc.201800944
82. Rocchigiani L (2015) Experimental Insights into the Structure and Reactivity of Frustrated
Lewis Pairs. Isr J Chem 55:134–149. https://doi.org/10.1002/ijch.201400139
83. Liu L, Lukose B, Jaque P, Ensing B (2019) Reaction Mechanism of Hydrogen Activation by
Frustrated Lewis Pairs. Green Energy Environ 4:20–28. https://doi.org/10.1016/j.gee.2018.
06.001
84. Hoffman BM, Lukoyanov D, Yang Z-Y, Dean DR, Seefeldt LC (2014) Mechanism of Nitrogen
Fixation by Nitrogenase: The Next Stage. Chem Rev 114:4041–4062. https://doi.org/10.1021/
cr400641x