Sabatier, P. How I have been led to the direct hydrogenation method by metallic catalysts. Ind. Eng. Chem. 18, 1005–1008 (1926).

Article  CAS  Google Scholar 

Bergius, F. Production of hydrogen from water and coal from cellulose at high temperatures and pressures. J. Soc. Chem. Ind. 32, 462–467 (1913).

Article  Google Scholar 

Knowles, W. S. Asymmetric hydrogenation. Acc. Chem. Res. 16, 106–112 (1983).

Article  CAS  Google Scholar 

Noyori, R. Asymmetric catalysis: science and opportunities (Nobel Lecture). Angew. Chem. Int. Ed. 41, 2008–2022 (2002).

Article  CAS  Google Scholar 

Wilkinson, G. & Birmingham, J. M. Biscyclopentadienylrhenium hydride—a new type of hydride. J. Am. Chem. Soc. 77, 3421–3422 (1955).

Article  CAS  Google Scholar 

Vaska, L. & DiLuzio, J. W. Activation of hydrogen by a transition metal complex at normal conditions leading to a stable molecular dihydride. J. Am. Chem. Soc. 84, 679–680 (1962).

Article  CAS  Google Scholar 

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, M(CO)3(PR3)2(H2) (M = molybdenum or tungsten; R = Cy or isopropyl). Evidence for a side-on bonded dihydrogen ligand. J. Am. Chem. Soc. 106, 451–452 (1984).

Article  CAS  Google Scholar 

Kubas, G. J., Unkefer, C. J., Swanson, B. I. & Fukushima, E. Molecular hydrogen complexes of the transition metals. 4. Preparation and characterization of M(CO)3(PR3)2(η2-H2) (M = molybdenum, tungsten) and evidence for equilibrium dissociation of the H–H bond to give MH2(CO)3(PR3)2. J. Am. Chem. Soc. 108, 7000–7009 (1986).

Article  CAS  Google Scholar 

Kubas, G. J. Fundamentals of H2 binding and reactivity on transition metals underlying hydrogenase function and H2 production and storage. Chem. Rev. 107, 4152–4205 (2007).

Article  CAS  PubMed  Google Scholar 

Crabtree, R. H. Dihydrogen complexation. Chem. Rev. 116, 8750–8769 (2016).

Article  CAS  PubMed  Google Scholar 

Lubitz, W., Ogata, H., Rüdiger, O. & Reijerse, E. Hydrogenases. Chem. Rev. 114, 4081–4148 (2014).

Article  CAS  PubMed  Google Scholar 

Kubas, G. J. Activation of dihydrogen and coordination of molecular H2 on transition metals. J. Organomet. Chem. 751, 33–49 (2014).

Article  CAS  Google Scholar 

Power, P. P. Main-group elements as transition metals. Nature 463, 171–177 (2010).

Article  CAS  PubMed  Google Scholar 

Melen, R. L. Frontiers in molecular p-block chemistry: from structure to reactivity. Science 363, 479–484 (2019).

Article  CAS  PubMed  Google Scholar 

Spikes, G. H., Fettinger, J. C. & Power, P. P. Facile activation of dihydrogen by an unsaturated heavier main group compound. J. Am. Chem. Soc. 127, 12232–12233 (2005).

Article  CAS  PubMed  Google Scholar 

Welch, G. C., Juan, R. R. S., Masuda, J. D. & Stephan, D. W. Reversible, metal-free hydrogen activation. Science 314, 1124–1126 (2006).

Article  CAS  PubMed  Google Scholar 

Frey, G. D., Lavallo, V., Donnadieu, B., Schoeller, W. W. & Bertrand, G. Facile splitting of hydrogen and ammonia by nucleophilic activation at a single carbon center. Science 316, 439–441 (2007).

Article  CAS  PubMed  Google Scholar 

Fischer, R. C. & Power, P. P. π-Bonding and the lone pair effect in multiple bonds involving heavier main group elements: developments in the new millennium. Chem. Rev. 110, 3877–3923 (2010).

Article  CAS  PubMed  Google Scholar 

Power, P. P. An update on multiple bonding between heavier main group elements: the importance of pauli repulsion, charge-shift character, and london dispersion force effects. Organometallics 39, 4127–4138 (2020).

Article  CAS  Google Scholar 

Hanusch, F., Groll, L. & Inoue, S. Recent advances of group 14 dimetallenes and dimetallynes in bond activation and catalysis. Chem. Sci. 12, 2001–2015 (2021).

Article  CAS  Google Scholar 

Stephan, D. W. & Erker, G. Frustrated Lewis pairs: metal-free hydrogen activation and more. Angew. Chem. Int. Ed. 49, 46–76 (2010).

Article  CAS  Google Scholar 

Stephan, D. W. The broadening reach of frustrated Lewis pair chemistry. Science 354, aaf7229 (2016).

Article  PubMed  Google Scholar 

Shan, C., Yao, S. & Driess, M. Where silylene–silicon centres matter in the activation of small molecules. Chem. Soc. Rev. 49, 6733–6754 (2020).

Article  CAS  PubMed  Google Scholar 

Hannah, T. J. & Chitnis, S. S. Ligand-enforced geometric constraints and associated reactivity in p-block compounds. Chem. Soc. Rev. 53, 764–792 (2024).

Article  CAS  PubMed  Google Scholar 

He, M., Hu, C., Wei, R., Wang, X.-F. & Liu, L. L. Recent advances in the chemistry of isolable carbene analogues with group 13–15 elements. Chem. Soc. Rev. 53, 3896–3951 (2024).

Article  CAS  PubMed  Google Scholar 

Hounjet, L. J. & Stephan, D. W. Hydrogenation by frustrated Lewis pairs: main group alternatives to transition metal catalysts?. Org. Process Res. Dev. 18, 385–391 (2014).

Article  CAS  Google Scholar 

Stephan, D. W. Diverse uses of the reaction of frustrated Lewis pair (FLP) with hydrogen. J. Am. Chem. Soc. 143, 20002–20014 (2021).

Article  CAS  PubMed  Google Scholar 

Lam, J., Szkop, K. M., Mosaferi, E. & Stephan, D. W. FLP catalysis: main group hydrogenations of organic unsaturated substrates. Chem. Soc. Rev. 48, 3592–3612 (2019).

Article  CAS  PubMed  Google Scholar 

Kötting, C. & Sander, W. Insertion of difluorovinylidene into hydrogen and methane. J. Am. Chem. Soc. 121, 8891–8897 (1999).

Article  Google Scholar 

Henkel, S., Ertelt, M. & Sander, W. Deuterium and hydrogen tunneling in the hydrogenation of 4-oxocyclohexa-2,5-dienylidene. Chem. Eur. J. 20, 7585–7588 (2014).

Article  CAS  PubMed  Google Scholar 

Henkel, S. & Sander, W. Activation of molecular hydrogen by a singlet carbene through quantum mechanical tunneling. Angew. Chem. Int. Ed. 54, 4603–4607 (2015).

Article  CAS  Google Scholar 

Bhagat, V., Meisner, J. & Wagner, J. P. Hydrogen activation by a σσ*-carbene through quantum tunneling. J. Am. Chem. Soc. 147, 35275–35282 (2025).

Article  CAS  PubMed  PubMed Central  Google Scholar 

Melaimi, M., Jazzar, R., Soleilhavoup, M. & Bertrand, G. Cyclic (alkyl)(amino)carbenes (CAACs): recent developments. Angew. Chem. Int. Ed. 56, 10046–10068 (2017).

Article  CAS  Google Scholar 

Soleilhavoup, M. & Bertrand, G. Cyclic (alkyl)(amino)carbenes (CAACs): stable carbenes on the rise. Acc. Chem. Res. 48, 256–266 (2015).

Article  CAS  PubMed  Google Scholar 

Bourissou, D., Guerret, O., Gabbaï, F. P. & Bertrand, G. Stable carbenes. Chem. Rev. 100, 39–92 (2000).

Article  CAS  PubMed