Dihydrogen Complexation

Chemical Reviews

Volumn 116, Issue 15, 2016, Pages 8750-8769

  Crabtree, Robert H ^a  

^a YALE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY;

COMPUTATIONAL STUDIES; HYDROGENASES; OXIDATIVE ADDITIONS; PROTON LOSS; REACTION SCHEMES; REACTIVITY PATTERN; SPECTROSCOPIC METHOD; STRUCTURAL TYPE;

SPECTROSCOPIC ANALYSIS;

COORDINATION COMPOUND; HYDROGEN; HYDROGENASE; NITROGENASE;

CATALYSIS; CHEMICAL MODEL; CHEMISTRY; ENZYME ACTIVE SITE; HYDROGEN BOND; NEUTRON DIFFRACTION; OXIDATION REDUCTION REACTION; PROTON NUCLEAR MAGNETIC RESONANCE;

CATALYSIS; CATALYTIC DOMAIN; COORDINATION COMPLEXES; HYDROGEN; HYDROGEN BONDING; HYDROGENASE; MODELS, CHEMICAL; NEUTRON DIFFRACTION; NITROGENASE; OXIDATION-REDUCTION; PROTON MAGNETIC RESONANCE SPECTROSCOPY;

EID: 84981508734     PISSN: 00092665     EISSN: 15206890     Source Type: Journal    
DOI: 10.1021/acs.chemrev.6b00037     Document Type: Review

References (189)

1. Kubas, G. J.; Ryan, R. R.; Swanson, B. I.; Vergamini, P. J.; Wasserman, H. J. Characterization of the First Examples of Isolable Molecular Hydrogen Complexes J. Am. Chem. Soc. 1984, 106, 451-452 10.1021/ja00314a049
2. 2 Production and Storage Chem. Rev. 2007, 107, 4152-4205 10.1021/cr050197j
3. Heinekey, D. M.; Oldham, W. J. Coordination Chemistry of Dihydrogen Chem. Rev. 1993, 93, 913-926 10.1021/cr00019a004
4. Jessop, P. G.; Morris, R. H. Reactions of Transition-Metal Dihydrogen Complexes Coord. Chem. Rev. 1992, 121, 155-284 10.1016/0010-8545(92)80067-2
5. Szymczak, N. K.; Tyler, D. R. Aspects of Dihydrogen Coordination Chemistry relevant to Reactivity in Aqueous Solution Coord. Chem. Rev. 2008, 252, 212-230 10.1016/j.ccr.2007.06.007
6. Crabtree, R. H. Dihydrogen Complexes: Their Structure and Chemistry Acc. Chem. Res. 1990, 23, 95-101 10.1021/ar00172a001
7. Kubas, G. J. Metal Dihydrogen and σ-bond Complexes; Kluwer/Plenum: New York, 2001.
8. Kubas, G. J. Activation of dihydrogen and Coordination of Molecular H2 on Transition Metals J. Organomet. Chem. 2014, 751, 33-39 10.1016/j.jorganchem.2013.07.041
9. Crabtree, R. H. Transition Metal Complexation of Sigma Bonds Angew. Chem., Int. Ed. Engl. 1993, 32, 789-805 10.1002/anie.199307891
10. Perutz, R. N.; Sabo-Etienne, S. The Sigma-CAM Mechanism: Sigma Complexes as the basis of Sigma-Bond Metathesis at Late-Transition-Metal Centers Angew. Chem., Int. Ed. 2007, 46, 2578-2592 10.1002/anie.200603224
11. Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 6 th ed.; J. Wiley and Sons: Hoboken, NJ, 2014; p 179.
12. Hashiguchi, S.; Fujii, A.; Takehara, J.; Ikariya, T.; Noyori, R. Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes J. Am. Chem. Soc. 1995, 117, 7562-7583 10.1021/ja00133a037
13. Maseras, F.; Lledós, A.; Clot, E.; Eisenstein, O. Transition Metal Polyhydrides: From Qualitative Ideas to Reliable Computational Studies Chem. Rev. 2000, 100, 601-636 10.1021/cr980397d
14. Devarajan, D.; Ess, D. H. Metal-Mediated Dihydrogen Activation. What Determines the Transition-State Geometry? Inorg. Chem. 2012, 51, 6367-6375 10.1021/ic3006426
15. 3-Catalyzed Direct Hydrogenation of Imines: Inherent and Thermally Induced Frustration J. Am. Chem. Soc. 2009, 131, 2029-2036 10.1021/ja809125r
16. Rokob, T. A.; Hamza, A.; Stirling, A.; Soos, T.; Papai, I. Turning Frustration into Bond Activation: a Theoretical Mechanistic Study on Heterolytic Hydrogen Splitting by Frustrated Lewis Pairs Angew. Chem., Int. Ed. 2008, 47, 2435-2438 10.1002/anie.200705586
17. Kubas, G. J. Metal-Dihydrogen and Sigma-Bond Coordination: the Consummate Extension of the Dewar-Chatt-Duncanson Model for Metal-Olefin Bonding J. Organomet. Chem. 2001, 635, 37-68 10.1016/S0022-328X(01)01066-X
18. 2+ Ions Bull. Soc. Chim. Fr. 1951, C71-C72
19. Pearson, R. G. Antisymbiosis and Trans Effect Inorg. Chem. 1973, 12, 712-713 10.1021/ic50121a052
20. Jalon, F. A.; Otero, A.; Manzano, B. R.; Villasenor, E.; Chaudret, B. First Observation in a Niobium Complex of the Rotation of a Coordinated H-D Molecule Blocked at the NMR Time-Scale J. Am. Chem. Soc. 1995, 117, 10123-10124 10.1021/ja00145a028
21. Cameron, T. M.; Ortiz, C. G.; Ghiviriga, I.; Abboud, K. A.; Boncella, J. M. The Synthesis and Reactivity of a Molybdenum (IV) Stretched-Dihydrogen Complex J. Am. Chem. Soc. 2002, 124, 922-923 10.1021/ja0169365
22. Connelly, S. J.; Chanez, A. G.; Kaminsky, W.; Heinekey, D. M. Characterization of a Palladium Dihydrogen Complex Angew. Chem., Int. Ed. 2015, 54, 5915-5918 10.1002/anie.201412076
23. 10 Ni-(H-H) Adduct as an Intermediate in H-H Oxidative Addition across a Ni-B Bond Angew. Chem., Int. Ed. 2014, 53, 1081-1086 10.1002/anie.201308175
24. 1,2,3 Complexes and Palladium Hydrides in Solid Argon and Neon J. Phys. Chem. A 2001, 105, 3052-3063 10.1021/jp003721t
25. 4 Complex in Solid Hydrogen J. Am. Chem. Soc. 2008, 130, 1972-1978 10.1021/ja077322o
26. 2CuF Inorg. Chem. 2013, 52, 816-822 10.1021/ic301941k
27. 2AgCl: A Spectroscopic Study of a Dihydrogen Complex J. Chem. Phys. 2014, 141, 114306-114306 10.1063/1.4895904
28. Nolan, S. P.; Marks, T. J. Organo-f-Element Thermochemistry-Implications for Organolanthanide Bonding and Reactivity J. Am. Chem. Soc. 1989, 111, 8538-8540 10.1021/ja00204a048
29. 2, ethylene, and acetylene to Bivalent Lanthanide Metallocenes Organometallics 2003, 22, 5447-5453 10.1021/om034206v
30. Armaroli, N.; Balzani, V. The Hydrogen Issue ChemSusChem 2011, 4, 21-36 10.1002/cssc.201000182
31. 8 Nickel Center: via Tetravalent Nickel? J. Am. Chem. Soc. 2010, 132, 910-916 10.1021/ja908674x
32. 2) Complex J. Am. Chem. Soc. 1997, 119, 9179-9190 10.1021/ja971009c
33. Dobereiner, G. E.; Nova, A.; Schley, N. D.; Hazari, N.; Miller, S. J.; Eisenstein, O.; Crabtree, R. H. Iridium-Catalyzed Hydrogenation of N-Heterocyclic Compounds under Mild Conditions by an Outer-Sphere Pathway J. Am. Chem. Soc. 2011, 133, 7547-7562 10.1021/ja2014983
34. Heinekey, D. M.; Lledós, A.; Lluch, J. M. Elongated Dihydrogen Complexes: what Remains of the H-H Bond? Chem. Soc. Rev. 2004, 33, 175-182 10.1039/B304879A
35. Maltby, P.; Schlaf, A. M.; Steinbeck, M.; Lough, A. J.; Morris, R. H.; Klooster, W. T.; Koetzle, T. F.; Srivastava, R. C. Dihydrogen with Frequency of Motion near the H-1 Larmor frequency. Solid-state Structures and Solution NMR Spectroscopy of some Osmium Complexes J. Am. Chem. Soc. 1996, 118, 5396-5407 10.1021/ja9529044
36. Gusev, D. G. Effect of Weak Interactions on the H···H Distance in Stretched Dihydrogen Complexes J. Am. Chem. Soc. 2004, 126, 14249-14257 and refs cited. 10.1021/ja0465956
37. 2Si Ansa Bridge on Classical versus Nonclassical Nature, Stability with Respect to Elimination of Dihydrogen, and Acidity J. Am. Chem. Soc. 2004, 126, 13054-13070 10.1021/ja047554c
38. Aresta, M.; Giannocarro, P.; Rossi, M.; Sacco, A. Hydrido Complexes of Fe(IV) and Fe(II) Inorg. Chim. Acta 1971, 5, 115-118 10.1016/S0020-1693(00)95893-6
39. 3 J. Am. Chem. Soc. 1986, 108, 3124-3125 10.1021/ja00271a063
40. Ashworth, J. V.; Singleton, E. Ionic Ruthenium(IV) Trihydrides as Intermediates in Heterolytic Fission of Dihydrogen by 5-Coordinate Hydridoruthenium(II) Cations J. Chem. Soc., Chem. Commun. 1976, 705-706 10.1039/C39760000705
41. Crabtree, R. H.; Lavin, M.; Bonneviot, L. Some Molecular-Hydrogen Complexes of Iridium J. Am. Chem. Soc. 1986, 108, 4032-4036 10.1021/ja00274a030
42. Sabo-Etienne, S.; Chaudret, B. Chemistry of bis(dihydrogen) Ruthenium Complexes and of their Derivatives Coord. Chem. Rev. 1998, 178-180, 381-407 10.1016/S0010-8545(98)00063-0
43. Chinn, M. S.; Heinekey, D. M.; Payne, N. G.; Sofield, C. D. Highly Reactive Dihydrogen Complexes of Ruthenium and Rhenium: Facile Heterolysis of Coordinated Dihydrogen Organometallics 1989, 8, 1824-1826 10.1021/om00109a042
44. Wulfsberg, G. Principles of Descriptive Inorganic Chemistry; Brooks/Cole: Monterey, CA, 1987.
45. +, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands J. Am. Chem. Soc. 1994, 116, 3375-3388 10.1021/ja00087a024
46. Morris, R. H.; Sawyer, J. F.; Shiralian, M.; Zubkowski, J. D. Two Molecular Hydrogen Complexes J. Am. Chem. Soc. 1985, 107, 5581-5582 10.1021/ja00305a071
47. Law, J. K.; Mellows, H.; Heinekey, D. M. H-H Distances in Elongated Transition Metal Dihydrogen Complexes: Effects of Temperature and Isotopic Substitution J. Am. Chem. Soc. 2001, 123, 2085-2086 10.1021/ja005536z
48. 1 Criterion for distinguishing between Classical and Nonclassical Transition Metal Hydrides J. Am. Chem. Soc. 1991, 113, 4173-4184 10.1021/ja00011a019
49. Hamilton, D. G.; Crabtree, R. H. An NMR Method of Distinguishing Classical from Nonclassical Transition Metal Polyhydrides J. Am. Chem. Soc. 1988, 110, 4126-4133 10.1021/ja00221a005
50. + M = Fe, Ru, R = Ph; M = Os, R = Et by Solution NMR Methods J. Am. Chem. Soc. 1988, 110, 7031-7036 10.1021/ja00229a015
51. 2-Dihydrogen Ligand on Longitudinal Nuclear Magnetic Resonance Relaxation Magn. Reson. Chem. 1997, 35, 243-250 and refs cited. 10.1002/(SICI)1097-458X(199704)35:4<243::AID-OMR61>3.0.CO;2-S
52. 2-Dihydrogen on the Brink of Homolytic Cleavage J. Am. Chem. Soc. 1991, 113, 3027-3039 10.1021/ja00008a035
53. Morris, R. H. Dihydrogen, dihydride and in between: NMR and structural properties of Iron Group Complexes Coord. Chem. Rev. 2008, 252, 2381-2394 10.1016/j.ccr.2008.01.010
54. 1 Data and Structure in a Series of Rhenium Polyhydride Complexes and the Contribution of M-H Dipole-Dipole Relaxation Magn. Reson. Chem. 1991, 29, S89-S96 10.1002/mrc.1260291317
55. Findlater, M.; Schultz, K. M.; Bernskoetter, W. H.; Cartwright-Sykes, A.; Heinekey, D. M.; Brookhart, M. Dihydrogen Complexes of Iridium and Rhodium Inorg. Chem. 2012, 51, 4672-4678 10.1021/ic202630x
56. Smith, D. A.; Herbert, D. E.; Walensky, J. R.; Ozerov, O. V. Monomeric Rhodium(II) Complexes Supported by a Diarylamido/ Bis(phosphine) PNP Pincer Ligand and Their Reactivity Toward Dihydrogen Organometallics 2013, 32, 2050-2058 10.1021/om300760j
57. 2) Complexes Organometallics 2010, 29, 3387-3391 10.1021/om100416w
58. 2+ J. Am. Chem. Soc. 2005, 127, 5632 10.1021/ja043011r
59. Gelabert, R.; Moreno, M.; Lluch, J. M. Elongated Dihydrogen Versus Compressed Dihydride Complexes: The Temperature Dependence of the H-D Spin-Spin Coupling Constant as a Criterion to Distinguish between them Chem.-Eur. J. 2005, 11, 6315 10.1002/chem.200500287
60. Law, J. K.; Mellows, H.; Heinekey, D. M. Synthesis and Spectroscopic Properties of Elongated Ruthenium Dihydrogen Complexes: Temperature and isotope Dependence of H-H distances J. Am. Chem. Soc. 2002, 124, 1024-1030 10.1021/ja0118284
61. Pons, V.; Heinekey, D. M. An Elongated Dihydrogen Complex of Iridium J. Am. Chem. Soc. 2003, 125, 8428 10.1021/ja035555j
62. Gelabert, R.; Moreno, M.; Lluch, J. M.; Lledós, A.; Pons, V.; Heinekey, D. M. Synthesis and properties of Compressed Dihydride Complexes of Iridium: Theoretical and spectroscopic investigations J. Am. Chem. Soc. 2004, 126, 8813-8822 10.1021/ja048775l
63. Göttker-Schnetmann, I.; Heinekey, D. M.; Brookhart, M. Temperature- and Solvent-Dependent Binding of Dihydrogen in Iridium Pincer Complexes J. Am. Chem. Soc. 2006, 128, 17114-17119 10.1021/ja065854j
64. + complex J. Am. Chem. Soc. 1997, 119, 9840-9847 10.1021/ja970838v
65. +-A Non-Classical Polyhydride Complex J. Chem. Soc., Chem. Commun. 1985, 1661-1662 10.1039/c39850001661
66. Saunders, M.; Kates, M. R. Isotopic Perturbation of Degeneracy-C-13 NMR spectra of Dimethylcyclopentyl and Dimethylnorbornyl cations J. Am. Chem. Soc. 1977, 99, 8070-8071 10.1021/ja00466a060
67. Bera, B.; Patil, Y. P.; Nethaji, M.; Jagirdar, B. R. Dynamics of H-atom Exchange in Stable cis-dihydrogen/hydride Complexes of Ruthenium(II) Dalton Trans. 2014, 43, 4726-33 10.1039/c3dt52575a
68. Nanishankar, H. V.; Dutta, S.; Nethaji, M.; Jagirdar, B. R. Dynamics of a cis-dihydrogen/hydride Complex of Iridium Inorg. Chem. 2005, 44, 6203-6210 10.1021/ic050266c
69. 1 NMR Relaxation Data in Solution Magn. Reson. Chem. 2004, 42, 66-70 and refs cited. 10.1002/mrc.1313
70. Sabo-Etienne, S.; Chaudret, B. Quantum mechanical exchange coupling in polyhydride and dihydrogen complexes Chem. Rev. 1998, 98, 2077-2091 10.1021/cr9601066
71. Heinekey, D. M. Transition metal dihydrogen complexes: isotope effects on reactivity and structure J. Labelled Compd. Radiopharm. 2007, 50, 1063-1071 and refs cited. 10.1002/jlcr.1385
72. Heinekey, D. M.; Payne, N. G.; Sofield, C. D. A Revisionist View Of Fluxionality In Metal Polyhydrides-The Role of Exchange Coupling Organometallics 1990, 9, 2643-2645 10.1021/om00160a005
73. Gründemann, S.; Limbach, H. H.; Rodriguez, V.; Donnadieu, B.; Sabo-Etienne, S.; Chaudret, B. Fast H-1 NMR Relaxation in some Ruthenium hydrides Ber. Bunsen-Ges. Phys. Chem. 1998, 102, 344-353 10.1002/bbpc.19981020310
74. 2 J. Am. Chem. Soc. 1995, 117, 1797-1799 10.1021/ja00111a018
75. Schloerer, N.; Pons, V.; Gusev, D. G.; Heinekey, D. M. Structure and Dynamics of a Compressed Dihydride Complex of Osmium Organometallics 2006, 25, 3481-3485 10.1021/om060284h
76. Teller, R. G.; Bau, R. Crystallographic Studies of Transition-Metal Hydride Complexes Struct. Bonding (Berlin) 1981, 44, 1-82 10.1007/BFb0111268
77. Bau, R. Structures of Transition-Metal Hydrides Determined by Neutron Diffraction Inorg. Chim. Acta 1997, 259, 27-50 10.1016/S0020-1693(97)89125-6
78. Mingos, D. M. P. A Historical Perspective on Dewar's Landmark Contribution to Organometallic Chemistry J. Organomet. Chem. 2001, 635, 1-8 10.1016/S0022-328X(01)01155-X
79. 2) Eur. J. Inorg. Chem. 2013, 2013, 5075-5080 10.1002/ejic.201301016
80. Oudeman, A.; Van Rantwijk, F.; Van Bekkum, H. J. A new Hydride of Osmium(II) J. Coord. Chem. 1974, 4, 1-7 10.1080/00958977408075872
81. 3 Inorg. Chem. 1999, 38, 4168-4174 10.1021/ic981402z
82. Yousufuddin, M.; BinWen, T.; Mason, S. A.; McIntyre, G. J.; Jia, G.; Bau, R. Neutron Diffraction Study of a ″Stretched″ Dihydrogen Ligand Angew. Chem., Int. Ed. 2005, 44, 7227-7230 10.1002/anie.200502297
83. Bürgi, H. B.; Dunitz, D. From Crystal Statics To Chemical-Dynamics Acc. Chem. Res. 1983, 16, 153-161 10.1021/ar00089a002
84. Baya, M.; Houghton, J.; Daran, J.-C.; Poli, R.; Male, L.; Albinati, A.; Gutman, M. Synthesis, Structure, and Electrochemical Properties of Sterically Protected Molybdenum Trihydride Redox Pairs: A Paramagnetic ″Stretched″ Dihydrogen Complex? Chem.-Eur. J. 2007, 13, 5347-5359 10.1002/chem.200700293
85. Eckert, J.; Kubas, G. J. Barrier to Rotation of the Dihydrogen Ligand in Metal-complexes J. Phys. Chem. 1993, 97, 2378-2584 10.1021/j100112a044
86. Li, S.; Hall, M. B.; Eckert, J.; Jensen, C. M.; Albinati, A. Transition Metal Polyhydride Complexes. Intramolecular Hydrogen Exchange in Octahedral Iridium(III) Dihydrogen Dihydride Complexes J. Am. Chem. Soc. 2000, 122, 2903-2910 10.1021/ja993877a
87. Ramirez-Cuesta, A. J.; Mitchell, P. C. H.; Parker, S. F. An Inelastic Neutron Scattering Study of the Interaction of Dihydrogen with the Cobalt Site of a Cobalt Aluminophosphate Catalyst-Two-Dimensional Quantum Rotation of Adsorbed Dihydrogen J. Mol. Catal. A: Chem. 2001, 167, 217-224 10.1016/S1381-1169(00)00509-4
88. Callear, S. K.; Ramirez-Cuesta, A. J.; David, W. I. F.; Millange, F.; Walton, R. I. High-Resolution Inelastic Neutron Scattering and Neutron Powder Diffraction Study of the Adsorption of Dihydrogen by the Cu(II) Metal-Organic Framework Material HKUST-1 Chem. Phys. 2013, 427, 9-17 10.1016/j.chemphys.2013.07.020
89. 2) in Liquefied Xenon Solution J. Am. Chem. Soc. 1986, 108, 2547-2553 10.1021/ja00270a010
90. 2) J. Am. Chem. Soc. 1990, 112, 1221-1233 10.1021/ja00159a051
91. Andrews, L. Matrix infrared Spectra and Density Functional Calculations of Transition Metal Hydrides and Dihydrogen Complexes Chem. Soc. Rev. 2004, 33, 123-132 10.1039/b210547k
92. Wang, X.; Andrews, L. Chromium Hydrides and Dihydrogen Complexes in Solid Neon, Argon, and Hydrogen: Matrix Infrared Spectra and Quantum Chemical Calculations J. Phys. Chem. A 2003, 107, 570-578 10.1021/jp026930h
93. Dryza, V.; Poad, B. L. J.; Bieske, E. J. Attaching Molecular Hydrogen to Metal Cations: Perspectives from Gas-Phase Infrared Spectroscopy Phys. Chem. Chem. Phys. 2012, 14, 14954-14965 10.1039/c2cp41622k
94. 2 Complex J. Phys. Chem. A 2009, 113, 6044-6048 10.1021/jp9031767
95. Prestipino, C.; Regli, L.; Vitillo, J. G.; Bonino, F.; Damin, A.; Lamberti, C.; Zecchina, A.; Solari, P. L.; Kongshaug, K. O.; Bordiga, S. Local Structure of Framework Cu(II) in HKUST-1 Metallorganic Framework: Spectroscopic Characterization upon Activation and Interaction with Adsorbates Chem. Mater. 2006, 18, 1337-1346 10.1021/cm052191g
96. 2(CO)X J. Am. Chem. Soc. 1993, 115, 8019-8023 10.1021/ja00071a012
97. 2+ Polyhydride Cluster as a Deactivation Product From Catalytic Glycerol Dehydrogenation Angew. Chem., Int. Ed. 2014, 53, 12808-12811 10.1002/anie.201407997
98. 2 to 5-Coordinate Tungsten Complexes Organometallics 1998, 17, 493-4939 10.1021/ja00237a011
99. 4, (M = Os, Ru and Fe) Dalton Trans. 2010, 39, 5527-5534 10.1039/c001161d
100. Esteruelas, M. A.; Oro, L. A. Dihydrogen Complexes As Homogeneous Reduction Catalysts Chem. Rev. 1998, 98, 577-588 10.1021/cr970322u
101. Gregson, D.; Howard, J. A. K.; Nicholls, J. N.; Spencer, J. L.; Turner, D. G. Synthesis and X-ray Crystal-structure of Tris(phenyldi-isopropylphosphine)-tungsten Hexahydride J. Chem. Soc., Chem. Commun. 1980, 572-573 10.1039/c39800000572
102. Leich, V.; Spaniol, T. P.; Okuda, J. Formation of a Cationic Calcium Hydride Cluster with a ″Naked″ Triphenylsilyl Anion by Hydrogenolysis of Bis(triphenylsilyl)calcium Inorg. Chem. 2015, 54, 4927-4933 10.1021/acs.inorgchem.5b00527
103. 3, the First Tris(pentamethylcyclopentadienyl) 5f-element Complex Angew. Chem., Int. Ed. Engl. 1997, 36, 774-776 10.1002/anie.199707741
104. Albeniz, A. C.; Schulte, G.; Crabtree, R. H. Facile Reversible Metalation in an Agostic Complex and Hydrogenolysis of a Metal Aryl Complex via a Dihydrogen Complex Organometallics 1992, 11, 242-249 10.1021/om00037a045
105. Esteruelas, M. A.; Larramona, C.; Oñate, E. Hydroosmiation of Allenes and Reductive Elimination of Olefin in Unsaturated Osmium(IV) Polyhydrides: Hydride versus Chloride Organometallics 2013, 32, 2567-2575 10.1021/om400041m
106. Jia, G.; Lin, C.; Lau, C. P. Reactions of Dihydrogen(norbornadiene) Complexes Eur. J. Inorg. Chem. 2003, 2003, 2551-2562 10.1002/ejic.200300054
107. Childs, G. I.; Cooper, A. I.; Nolan, T. F.; Carrott, M. J.; George, M. W.; Poliakoff, M. An Investigation into the Photocatalytic Hydrogenation of Norbornadiene and Dimethylfumarate using Polyethylene Matrices at Low Temperature and High Pressure J. Am. Chem. Soc. 2001, 123, 6857-6866 10.1021/ja004345t
108. 3 Organometallics 1990, 9, 2985-2992 10.1021/om00161a030
109. 3 Organometallics 1996, 15, 2611-2618 10.1021/om950881w
110. Orchin, M.; Rupilius, W. Mechanism of Oxo Reaction Catal. Rev.: Sci. Eng. 1972, 6, 85-101 10.1080/01614947208078692
111. 8 Ir(I) Complex Yields a trans Ir(III) Dihydride J. Am. Chem. Soc. 2010, 132, 4534-4540 10.1021/ja100168w
112. Hebden, T. J.; Goldberg, K. I.; Heinekey, D. M.; Zhang, X.; Emge, T. J.; Goldman, A. S.; Krogh-Jespersen, K. Dihydrogen/Dihydride or Tetrahydride? An Experimental and Computational Investigation of Pincer Iridium Polyhydrides Inorg. Chem. 2010, 49, 1733-1742 10.1021/ic902163w
113. Hebden, T. J.; St. John, A. J.; Gusev, D. G.; Kaminsky, W.; Goldberg, K. I.; Heinekey, D. M. Preparation of a Dihydrogen Complex of Cobalt Angew. Chem., Int. Ed. 2011, 50, 1873-1876 10.1002/anie.201005281
114. +, the ″Enfant Terrible″ of Chemical Structures Science 2015, 347, 1313-1314 10.1126/science.aaa6935
115. Carreón-Macedo, J.-L.; Harvey, J. N. Do Spin State Changes Matter in Organometallic Chemistry? A Computational Study J. Am. Chem. Soc. 2004, 126, 5789-5797 10.1021/ja049346q
116. 2 Alkyl Complexes Of Molybdenum And Tungsten that Contain the Trimethylsilyl-Substituted Triamidoamine Ligand J. Am. Chem. Soc. 1995, 117, 6609-6610 10.1021/ja00129a032
117. Parkin, G. Temperature-Dependent Transitions Between Normal and Inverse Isotope Effects Pertaining to the Interaction of H-H and C-H Bonds with Transition Metal Center Acc. Chem. Res. 2009, 42, 315-325 10.1021/ar800156h
118. 2-Dihydrogen Complexes: Hydrogen-Binding Modes and Mechanistic Studies by DFT Calculations Organometallics 2007, 26, 508-513 10.1021/om060797o
119. + and Related Compounds J. Organomet. Chem. 2000, 609, 29-35 10.1016/S0022-328X(00)00350-8
120. 5 (M = Fe, Ru, Os) J. Phys. Chem. A 2012, 116, 2529-2535 10.1021/jp204776a
121. Kubas, G. J. Catalytic Processes Involving Dihydrogen Complexes Catal. Lett. 2005, 104, 79-101 10.1007/s10562-005-7440-3
122. Zeng, G.; Sakaki, S.; Fujita, K.-i.; Sano, H.; Yamaguchi, R. Efficient Catalyst for Acceptor less Alcohol Dehydrogenation: Interplay of Theoretical and Experimental Studies ACS Catal. 2014, 4, 1010-1020 10.1021/cs401101m
123. Dyer, H.; Picot, A.; Vendier, L.; Auffrant, A.; Le Floch, P.; Sabo-Etienne, S. Tridentate and Tetradentate Iminophosphorane-Based Ruthenium Complexes in Catalytic Transfer Hydrogenation of Ketones Organometallics 2011, 30, 1478-1486 10.1021/om101058m
124. Manca, G.; Mellone, I.; Bertini, F.; Peruzzini, M.; Rosi, L.; Mellmann, D.; Junge, H.; Beller, M.; Ienco, A.; Gonsalvi, L. Inner- versus Outer-Sphere Ru-Catalyzed Formic Acid Dehydrogenation: A Computational Study Organometallics 2013, 32, 7053-7064 10.1021/om400761t
125. 2 Production, Utilization, and Storage for Future Energy J. Organomet. Chem. 2009, 694, 2648-2653 10.1016/j.jorganchem.2009.05.027
126. Sandhya, K. S.; Suresh, C. H. Water Splitting Promoted by a Ruthenium(II) PNN Complex: An Alternate Pathway through a Dihydrogen Complex for Hydrogen Production Organometallics 2011, 30, 3888-3891 10.1021/om200046u
127. Hamon, P.; Toupet, L.; Hamon, J. R.; Lapinte, C. Novel Diamagnetic and Paramagnetic Iron(II), Iron(III), and Iron(IV) Classical and Nonclassical Hydrides Organometallics 1992, 11, 1429-1431 10.1021/om00040a001
128. 2(μ-H) Organometallics 2010, 29, 1045-1048 10.1021/om901005k
129. Schlapbach, L.; Züttel, A. Hydrogen-Storage Materials for Mobile Applications Nature 2001, 414, 353-358 10.1038/35104634
130. Crabtree, R. H. Hydrogen Storage in Liquid Organic Heterocycles Energy Environ. Sci. 2008, 1, 134-138 10.1039/b805644g
131. Panella, B.; Hirscher, M.; Roth, S. Hydrogen Adsorption in Different Carbon Nanostructures Carbon 2005, 43, 2209-2214 10.1016/j.carbon.2005.03.037
132. Hoang, T. K. A.; Antonelli, D. M. Exploiting the Kubas Interaction in the Design of Hydrogen Storage Materials Adv. Mater. 2009, 21, 1787-1800 10.1002/adma.200802832
133. Durgun, E.; Ciraci, S.; Yildirim, T. Functionalization of Carbon-Based Nanostructures with Light Transition-Metal Atoms for Hydrogen Storage Phys. Rev. B: Condens. Matter Mater. Phys. 2008, 77, 085405-085405 10.1103/PhysRevB.77.085405
134. Huang, C.-C.; Li, Y.-H.; Wang, Y.-W.; Chen, C.-H. Hydrogen Storage in Cobalt-Embedded Ordered Mesoporous Carbon Int. J. Hydrogen Energy 2013, 38, 3994-4002 10.1016/j.ijhydene.2013.01.081
135. Skipper, C. V. J.; Hamaed, A.; Antonelli, D. M.; Kaltsoyannis, N. The Kubas interaction in M(II) (M = Ti, V, Cr) Hydrazine-Based Hydrogen Storage Materials Dalton Trans. 2012, 41, 8515-8523 10.1039/c2dt30383c
136. Beheshti, E.; Nojeh, A.; Servati, P. A First-Principles Study of Calcium-Decorated, Boron-Doped Graphene for High Capacity Hydrogen Storage Carbon 2011, 49, 1561-1567 10.1016/j.carbon.2010.12.023
137. Singh, A. K.; Yakobson, B. I. First Principles Calculations of H-storage in Sorption Materials J. Mater. Sci. 2012, 47, 7356-7366 and refs cited. 10.1007/s10853-012-6551-7
138. Lin, X.; Telepeni, I.; Blake, A. J.; Dailly, A.; Brown, C. M.; Simmons, J. M.; Zoppi, M.; Walker, G. S.; Thomas, K. M.; Mays, T. J.; Hubberstey, P.; Champness, N. R.; Schröder, M. High Capacity Hydrogen Adsorption in Cu(II) Tetracarboxylate Framework Materials: The Role of Pore Size, Ligand Functionalization, and Exposed Metal Sites J. Am. Chem. Soc. 2009, 131, 2159-2171 10.1021/ja806624j
139. 2 to Open Metal Sites in a Metal-Organic Framework: A Symmetry-Adapted Perturbation Theory Analysis J. Phys. Chem. A 2014, 118, 7411-7417 10.1021/jp412779q
140. Getman, R. B.; Bae, Y.-S.; Wilmer, C. E.; Snurr, R. Q. Review and Analysis of Molecular Simulations of Methane, Hydrogen, and Acetylene Storage in Metal-Organic Frameworks Chem. Rev. 2012, 112, 703-723 10.1021/cr200217c
141. Hoang, T. K. A.; Webb, M. I.; Mai, H. V.; Hamaed, A.; Walsby, C. J.; Trudeau, M.; Antonelli, D. M. Design and Synthesis of Vanadium Hydrazide Gels for Kubas-Type Hydrogen Adsorption: A New Class of Hydrogen Storage Materials J. Am. Chem. Soc. 2010, 132, 11792-11798 10.1021/ja104926h
142. 3 clusters J. Alloys Compd. 2014, 588, 144-152 10.1016/j.jallcom.2013.10.147
143. Morris, L.; Trudeau, M. L.; Reed, D.; Book, D.; Antonelli, D. M. Thermodynamically Neutral Kubas-Type Hydrogen Storage Using Amorphous Cr(III) Alkyl Hydride Gels Phys. Chem. Chem. Phys. 2015, 17, 9480-9487 10.1039/C5CP00412H
144. Hoang, T. K. A.; Morris, L.; Reed, D.; Book, D.; Trudeau, M. L.; Antonelli, D. M. Observation of TiH5 and TiH7 in Bulk-Phase TiH3 Gels for Kubas-Type Hydrogen Storage Chem. Mater. 2013, 25, 4765-4771 10.1021/cm402853k
145. Stephan, D. W. Frustrated Lewis Pairs: From Concept to Catalysis Acc. Chem. Res. 2015, 48, 306-316 10.1021/ar500375j
146. Welch, G. C.; San Juan, R. R.; Matsuda, J. D.; Stephan, D. W. Reversible Metal-Free Hydrogen Activation Science 2006, 314, 1124-1126 10.1126/science.1134230
147. Welch, G. C.; Stephan, D. W. Facile Heterolytic Cleavage of Dihydrogen by Phosphines and Boranes J. Am. Chem. Soc. 2007, 129, 1880-1881 10.1021/ja067961j
148. Oestreich, M.; Hermeke, J.; Mohr, J. A Unified Survey of Si-H and H-H bond Activation Catalysed by Electron-Deficient Boranes Chem. Soc. Rev. 2015, 44, 2202-2220 10.1039/C4CS00451E
149. Grimme, S.; Kruse, H.; Goerigk, L.; Erker, G. The Mechanism of Dihydrogen Activation by Frustrated Lewis Pairs Revisited Angew. Chem., Int. Ed. 2010, 49, 1402-1405 10.1002/anie.200905484
150. 2 Elimination and Activation Reactions J. Phys. Chem. A 2009, 113, 8108-8114 10.1021/jp903059w
151. Houghton, A. Y.; Karttunen, V. A.; Piers, W. E.; Tuononen, H. M. Hydrogen Activation with Perfluorinated Organoboranes Chem. Commun. 2014, 50, 1295-1296 10.1039/C3CC48796B
152. Houghton, A. Y.; Hurmalainen, J.; Mansikkamaki, A.; Piers, W. E.; Tuononen, H. M. Direct Observation of a Borane-Silane Complex Involved in Frustrated Lewis-Pair-Mediated Hydrosilylations Nat. Chem. 2014, 6, 983-988 10.1038/nchem.2063
153. Wang, Y.; Ma, J. Silylenes and Germylenes: The Activation of H-H bond in Hydrogen Molecule J. Organomet. Chem. 2009, 694, 2567-2575 10.1016/j.jorganchem.2009.03.051
154. Crabtree, R. H. Dihydrogen Binding in Hydrogenase and Nitrogenase Inorg. Chim. Acta 1986, 125, L7-L8 10.1016/S0020-1693(00)85472-9
155. Leigh, G. J. Protonation of Coordinated Dinitrogen Acc. Chem. Res. 1992, 25, 177-181 10.1021/ar00016a001
156. Koch, S.; Jiang, J. F. Did nature discover Greg Kubas chemistry 3 billion years ago? Chemistry of the unprecedented Fe(CO)(CN)(X) centers in NiFe and Fe-only hydrogenase enzymes Abs. Pap. Am. Chem. Soc. 2001, 221, U724-U724
157. Gordon, J. C.; Kubas, G. J. Perspectives on How Nature Employs the Principles of Organometallic Chemistry in Dihydrogen Activation in Hydrogenases Organometallics 2010, 29, 4682-4701 10.1021/om100436c
158. Kubas, G. J. The Art and Beauty of Inorganic Synthesis on the Path to Discovery: Transition Metal Coordination and Activation of Sulfur Dioxide and Dihydrogen Comments Inorg. Chem. 2012, 33, 102-121 10.1080/02603594.2013.772896
159. Hoffman, B. M.; Lukoyanov, D.; Yang, Z. Y.; Dean, D. R.; Seefeldt, L. C. Mechanism of Nitrogen Fixation by Nitrogenase: The Next Stage Chem. Rev. 2014, 114, 4041-4062 10.1021/cr400641x
160. Pavlov, M.; Siegbahn, P. E. M.; Blomberg, M. R. A.; Crabtree, R. H. Mechanism of H-H Activation by Nickel-Iron Hydrogenase J. Am. Chem. Soc. 1998, 120, 548-555 10.1021/ja971681+
161. Yang, X.; Hall, M. B. Monoiron Hydrogenase Catalysis J. Am. Chem. Soc. 2009, 131, 10901-10908 10.1021/ja902689n
162. Liu, T. B.; Wang, X.; Hoffmann, C.; Dubois, D. L.; Bullock, R. M. Heterolytic Cleavage of Hydrogen by an Iron Hydrogenase Model: An Fe-H···H-N Dihydrogen Bond Characterized by Neutron Diffraction Angew. Chem., Int. Ed. 2014, 53, 5300-5304 10.1002/anie.201402090
163. 2 Organometallics 2015, 34, 2747-2764 10.1021/om501289f
164. Bullock, R. M.; Helm, M. L. ″ Molecular Electrocatalysts for Oxidation of Hydrogen Using Earth-Abundant Metals: Shoving Protons Around with Proton Relays Acc. Chem. Res. 2015, 48, 2017-2026 10.1021/acs.accounts.5b00069
165. Darmon, J. M.; Kumar, N.; Hulley, E. B.; Weiss, C. J.; Raugei, S.; Bullock, R. M.; Helm, M. L. Increasing the Rate Of Hydrogen Oxidation Without Increasing the Overpotential: a Bio-Inspired Iron Molecular Electrocatalyst With An Outer Coordination Sphere Proton Relay Chem. Sci. 2015, 6, 2737-2745 10.1039/C5SC00398A
166. Liu, T.; Chen, S.; O'Hagan, M. J.; Rakowski DuBois, M.; Bullock, R. M.; DuBois, D. L. Synthesis, Characterization, and Reactivity of Fe Complexes Containing Cyclic Diazadiphosphine Ligands: The Role of the Pendant Base in Heterolytic Cleavage of H2 J. Am. Chem. Soc. 2012, 134, 6257-6272 10.1021/ja211193j
167. Custelcean, R.; Jackson, J. E. Dihydrogen bonding: Structures, Energetics, and Dynamics Chem. Rev. 2001, 101, 1963-1980 10.1021/cr000021b
168. Belkova, N. V.; Epstein, L. M.; Filippov, O. A.; Shubina, E. S. Hydrogen and Dihydrogen Bonds in the Reactions of Metal Hydrides Chem. Rev. 2016, 116, 100-120
169. 3} with Acids in Tetrahydrofuran J. Chem. Soc., Dalton Trans. 1998, 745-750 10.1039/a707491c
170. 2 Formation with Protic Donors J. Organomet. Chem. 2010, 695, 382-391 10.1016/j.jorganchem.2009.10.036
171. 2 J. Am. Chem. Soc. 1994, 116, 8356-8357 and refs cited. 10.1021/ja00097a049
172. 2 J. Am. Chem. Soc. 2013, 135, 11736-11739 10.1021/ja405755j
173. Chinn, M. S.; Heinekey, D. M. Dihydrogen Complexes of Ruthenium 2. Kinetic and Thermodynamic Considerations Affecting Product Distribution J. Am. Chem. Soc. 1990, 112, 5166-5175 10.1021/ja00169a026
174. 3)H: Is the Metal or the Hydride the Kinetic Site? J. Am. Chem. Soc. 2000, 122, 12235-12242 10.1021/ja002395s
175. 3OD Organometallics 2012, 31, 3087-3100 10.1021/om300015j
176. 2 Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane Organometallics 2013, 32, 3053-3062 10.1021/om400281v
177. Gunanathan, C.; Milstein, D. Bond Activation and Catalysis by Ruthenium Pincer Complexes Chem. Rev. 2014, 114, 12024-12087 10.1021/cr5002782
178. + J. Am. Chem. Soc. 2007, 129, 6608-6618 10.1021/ja070939l
179. - on the Rotation of Coordinated Dihydrogen and the F-19 Relaxation Time Chem. Commun. 2009, 4563-4565 10.1039/b906330g
180. Morris, R. H. Estimating the Acidity of Transition Metal Hydride And Dihydrogen Complexes by Adding Ligand Acidity Constants,″ J. Am. Chem. Soc. 2014, 136, 1948-1959 10.1021/ja410718r
181. + J. Am. Chem. Soc. 1992, 114, 5905-5906 10.1021/ja00040a089
182. Matthews, S. L.; Heinekey, D. M. Photochemical Generation of Dihydrogen Complexes of Cr and W J. Am. Chem. Soc. 2006, 128, 2615-2620 10.1021/ja057912r
183. 2O as the Only Deuterium Source. Theoretical and Experimental Demonstration of a Ru-H/D+ Exchange as the Key Step ACS Catal. 2014, 4, 1040-1053 10.1021/cs401224g
184. 3) ChemPlusChem 2014, 79, 1316-1325 10.1002/cplu.201402108
185. + (M = Fe, Ru, Os) Organometallic Complexes for Hydrogen Storage Applications J. Phys. Chem. C 2014, 118, 1783-1792 10.1021/jp409739b
186. Connelly, S. J.; Zimmerman, A. C.; Kaminsky, W.; Heinekey, D. M. Synthesis, Structure, and Reactivity of a Nickel Dihydrogen Complex Chem.-Eur. J. 2012, 18, 15932-15934 and refs cited. 10.1002/chem.201203675
187. 2 Adducts of Cationic Nickel(II) Chem. Sci. 2012, 3, 1313-1318 10.1039/c2sc01033j
188. 2 Complex J. Am. Chem. Soc. 2014, 136, 14998-15009 10.1021/ja508117h
189. Suess, D. L. M.; Tsay, C.; Peters, J. C. Dihydrogen Binding to Isostructural S = 1/2 and S = 0 Cobalt Complexes J. Am. Chem. Soc. 2012, 134, 14158-14164 10.1021/ja305248f