5 Mechanistic Insight into the Hydrogen Activation by Frustrated Lewis Pairs
205
33. Rokob TA, Hamza A, Pápai I (2009) Rationalizing the Reactivity of Frustrated Lewis Pairs:
Thermodynamics of H 2 Activation and the Role of Acid-Base Properties. J Am Chem Soc
131:10701–10710. https://doi.org/10.1021/ja903878z
34. Zeonjuk LL, Vankova N, Mavrandonakis A, Heine T, Röschenthaler GV, Eicher J (2013) On
the Mechanism of Hydrogen Activation by Frustrated Lewis Pairs. Chem Eur J 9:17413–
17424. https://doi.org/10.1002/chem.201302727
35. Skara G, Pinter B, Top J, Geerlings P, De Proft F, De Vleeschouwer F (2015) Conceptual
Quantum Chemical Analysis of Bonding and Noncovalent Interactions in the Formation of
Frustrated Lewis Pairs. Chem Eur J 21:5510–5519. https://doi.org/10.1002/chem.201405891
36. Skara G, De Vleeschouwer F, Geerlings P, De Proft F, Pinter B (2017) Heterolytic Splitting of
Molecular Hydrogen by Frustrated and Classical Lewis Pairs: A Unified Reactivity Concept.
Scientific Reports 7:16024. https://doi.org/10.1038/s41598-017-16244-1
37. Ilic S, Alherz A, Musgrave CB, Glusac KD (2018) Thermodynamics and Kinetic Hydricities
of Metal-Free Hydrides. Chem Soc Rev 47:2809–2836. https://doi.org/10.1039/C7CS00171A
38. Bakó I, Stirling A, Bálint S, Pápai I (2012) Association of Frustrated Phosphine-Borane Pairs
in Toluene: Molecular Dynamics Simulations. Dalton Trans 41:9023–9025. https://doi.org/
10.1039/C2DT30370A
39. Rocchigiani L, Ciancaleoni G, Zuccaccia C, Macchioni A (2014) Probing the Association
of Frustrated Phosphine-Borane Lewis Pairs in Solution by NMR Spectroscopy. J Am Chem
Soc 136:112–115. https://doi.org/10.1021/ja4119169
40. (a) Squires GL (1997) Introduction to the Theory of Thermal Neutron Scattering. Dover Publications ISBN 048669447. (b) Brown LC, Hogg JM, Gilmore M, Moura L, Imberti S, Gärtner
S, Gunaratne HQN, O’Donnell RJ, Artioli N, Holbrey JD, Swad´ zba-Kwa´ sny M (2018) Frustrated Lewis Pairs in Ionic Liquids and Molecular Solvents - A Neutron Scattering and NMR
Study of Encounter Complexes. Chem Commun 54:8689–8692. https://doi.org/10.1039/C8C
C03794A
41. Lathem AP, Rinne BL, Maldonado MA, Heiden ZM (2017) Comparison of Intramolecular
and Intermolecular Ammonium- and Phosphonium-Borohydrides in Hydrogen, Proton, and
Hydride Transfer Reactions. Eur J Inorg Chem 2017:2032–2039. https://doi.org/10.1002/ejic.
201700016
42. Spies P, Erker G, Kehr G, Bergander K, Fröhlich R, Grimme S, Stephan DW (2007)
Rapid Intramolecular Heterolytic Dihydrogen Activation by a Four-Membered Heterocyclic Phosphane–Borane Adduct. Chem Commun 2:5072–5074. https://doi.org/10.1039/
B710475H
43. Özgün T, Ye KY, Daniliuc CG, Wibbeling B, Liu L, Grimme S, Kehr G, Erker
G (2016) Why Does the Intramolecular Trimethylene-Bridged Frustrated Lewis Pair
Mes 2 PCH 2 CH 2 CH 2 B(C 6 F 5 ) 2 Not Activate Dihydrogen? Chem Eur J 22:5988–5995. https://
doi.org/10.1002/chem.201505200
44. Axenov KV, Mömming CM, Kehr G, Fröhlich R, Erker G (2010) Structure and Dynamic
Features of an Intramolecular Frustrated Lewis Pair. Chem Eur J 16:14069–14073. https://
doi.org/10.1002/chem.201001814
45. Ye KY, Daniliuc CG, Dong S, Kehr G, Erker G (2017) Frustrated Lewis Pair Behavior of
an Open, Noninteracting Phosphane/Borane Pair at a Rigid Organic Framework: Exploring
Decisive Factors for FLP Activity. Organometallics 36:5003–5012. https://doi.org/10.1021/
acs.organomet.7b00819
46. Liu L, Petkov PS, Heine T, Röschenthaler GV, Eicher J, Vankova N (2015) Are Intramolecular
Frustrated Lewis Pairs also Intramolecular Catalysts? A Theoretical Study on H 2 Activation.
Phys Chem Chem Phys 17:10687–10698. https://doi.org/10.1039/C5CP00368G
47. Özgün T, Bergander K, Liu L, Daniliuc CG, Grimme S, Kehr G, Erker G (2016) A Frustrated
Phosphane-Borane Lewis Pair and Hydrogen: A Kinetics Study. Chem Eur J 22:11958–
11961. https://doi.org/10.1002/chem.201603050
48. Rajeev R, Sunoj RB (2009) On the Origin of Reversible Hydrogen Activation by PhosphineBoranes. Chem Eur J 15:12846–12855. https://doi.org/10.1002/chem.200900663
49. Cabrera-Trujillo JJ, Fernández I (2018) Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E-CH 2 -E’ Frustrated Lewis Pairs. Chem Eur J 24:17823–21783. https://doi.
org/10.1002/chem.201804198
205
33. Rokob TA, Hamza A, Pápai I (2009) Rationalizing the Reactivity of Frustrated Lewis Pairs:
Thermodynamics of H 2 Activation and the Role of Acid-Base Properties. J Am Chem Soc
131:10701–10710. https://doi.org/10.1021/ja903878z
34. Zeonjuk LL, Vankova N, Mavrandonakis A, Heine T, Röschenthaler GV, Eicher J (2013) On
the Mechanism of Hydrogen Activation by Frustrated Lewis Pairs. Chem Eur J 9:17413–
17424. https://doi.org/10.1002/chem.201302727
35. Skara G, Pinter B, Top J, Geerlings P, De Proft F, De Vleeschouwer F (2015) Conceptual
Quantum Chemical Analysis of Bonding and Noncovalent Interactions in the Formation of
Frustrated Lewis Pairs. Chem Eur J 21:5510–5519. https://doi.org/10.1002/chem.201405891
36. Skara G, De Vleeschouwer F, Geerlings P, De Proft F, Pinter B (2017) Heterolytic Splitting of
Molecular Hydrogen by Frustrated and Classical Lewis Pairs: A Unified Reactivity Concept.
Scientific Reports 7:16024. https://doi.org/10.1038/s41598-017-16244-1
37. Ilic S, Alherz A, Musgrave CB, Glusac KD (2018) Thermodynamics and Kinetic Hydricities
of Metal-Free Hydrides. Chem Soc Rev 47:2809–2836. https://doi.org/10.1039/C7CS00171A
38. Bakó I, Stirling A, Bálint S, Pápai I (2012) Association of Frustrated Phosphine-Borane Pairs
in Toluene: Molecular Dynamics Simulations. Dalton Trans 41:9023–9025. https://doi.org/
10.1039/C2DT30370A
39. Rocchigiani L, Ciancaleoni G, Zuccaccia C, Macchioni A (2014) Probing the Association
of Frustrated Phosphine-Borane Lewis Pairs in Solution by NMR Spectroscopy. J Am Chem
Soc 136:112–115. https://doi.org/10.1021/ja4119169
40. (a) Squires GL (1997) Introduction to the Theory of Thermal Neutron Scattering. Dover Publications ISBN 048669447. (b) Brown LC, Hogg JM, Gilmore M, Moura L, Imberti S, Gärtner
S, Gunaratne HQN, O’Donnell RJ, Artioli N, Holbrey JD, Swad´ zba-Kwa´ sny M (2018) Frustrated Lewis Pairs in Ionic Liquids and Molecular Solvents - A Neutron Scattering and NMR
Study of Encounter Complexes. Chem Commun 54:8689–8692. https://doi.org/10.1039/C8C
C03794A
41. Lathem AP, Rinne BL, Maldonado MA, Heiden ZM (2017) Comparison of Intramolecular
and Intermolecular Ammonium- and Phosphonium-Borohydrides in Hydrogen, Proton, and
Hydride Transfer Reactions. Eur J Inorg Chem 2017:2032–2039. https://doi.org/10.1002/ejic.
201700016
42. Spies P, Erker G, Kehr G, Bergander K, Fröhlich R, Grimme S, Stephan DW (2007)
Rapid Intramolecular Heterolytic Dihydrogen Activation by a Four-Membered Heterocyclic Phosphane–Borane Adduct. Chem Commun 2:5072–5074. https://doi.org/10.1039/
B710475H
43. Özgün T, Ye KY, Daniliuc CG, Wibbeling B, Liu L, Grimme S, Kehr G, Erker
G (2016) Why Does the Intramolecular Trimethylene-Bridged Frustrated Lewis Pair
Mes 2 PCH 2 CH 2 CH 2 B(C 6 F 5 ) 2 Not Activate Dihydrogen? Chem Eur J 22:5988–5995. https://
doi.org/10.1002/chem.201505200
44. Axenov KV, Mömming CM, Kehr G, Fröhlich R, Erker G (2010) Structure and Dynamic
Features of an Intramolecular Frustrated Lewis Pair. Chem Eur J 16:14069–14073. https://
doi.org/10.1002/chem.201001814
45. Ye KY, Daniliuc CG, Dong S, Kehr G, Erker G (2017) Frustrated Lewis Pair Behavior of
an Open, Noninteracting Phosphane/Borane Pair at a Rigid Organic Framework: Exploring
Decisive Factors for FLP Activity. Organometallics 36:5003–5012. https://doi.org/10.1021/
acs.organomet.7b00819
46. Liu L, Petkov PS, Heine T, Röschenthaler GV, Eicher J, Vankova N (2015) Are Intramolecular
Frustrated Lewis Pairs also Intramolecular Catalysts? A Theoretical Study on H 2 Activation.
Phys Chem Chem Phys 17:10687–10698. https://doi.org/10.1039/C5CP00368G
47. Özgün T, Bergander K, Liu L, Daniliuc CG, Grimme S, Kehr G, Erker G (2016) A Frustrated
Phosphane-Borane Lewis Pair and Hydrogen: A Kinetics Study. Chem Eur J 22:11958–
11961. https://doi.org/10.1002/chem.201603050
48. Rajeev R, Sunoj RB (2009) On the Origin of Reversible Hydrogen Activation by PhosphineBoranes. Chem Eur J 15:12846–12855. https://doi.org/10.1002/chem.200900663
49. Cabrera-Trujillo JJ, Fernández I (2018) Influence of the Lewis Acid/Base Pairs on the Reactivity of Geminal E-CH 2 -E’ Frustrated Lewis Pairs. Chem Eur J 24:17823–21783. https://doi.
org/10.1002/chem.201804198