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• W3033584346 abstract "Challenges and opportunities:•Design and adapt frustrated Lewis pairs (FLPs) to provide increased activity for homogeneous or heterogeneous catalysis of hydrogenation of industrially important substrates.•Design FLPs that are capable of activating substrates containing strong bonds of interest (e.g., N2, CO, or CH4).•Uncover unprecedented catalytic activity of FLPs and/or exploit the concept of FLPs to develop main-group catalysts that are distinct from or complementary to that of traditional transition-metal catalysts. This Perspective describes the development of the field of catalysis and the advent of metal-free catalysis by focusing on the use of main-group species as frustrated Lewis pair catalysts. In addition to outlining the major advances in this area, it also discusses how these advances could evolve and affect the future of catalysis. This Perspective describes the development of the field of catalysis and the advent of metal-free catalysis by focusing on the use of main-group species as frustrated Lewis pair catalysts. In addition to outlining the major advances in this area, it also discusses how these advances could evolve and affect the future of catalysis. Since the early 20th century, catalysis as a field has evolved rapidly from fundamental science to advanced chemical technologies. Indeed, advances in catalyst technology have transformed our lives and our society. Catalysis has given us the ability to produce fertilizers that feed millions of people worldwide and efficiently process petroleum for fuel and chemicals and has afforded avenues for producing drugs, materials, and agrochemicals with exquisite precision. The impact of catalysis has also been recognized with seven Nobel Prizes. The first was in 1909 to Ostwald,1Ostwald W. Catalysis. Chem. Ztg. 1910; 34: 397-399Google Scholar who formulated the initial fundamentals of the chemistry, and Sabatier was awarded the prize 3 years later for his work in heterogeneous hydrogenations.2Sabatier P. Kubota B. Hydrogenations catalytique sur le cuivre.Compt. Rend. 1921; 172: 733-736Google Scholar In 1918, Haber3Haber F. The production of ammonia from nitrogen and hydrogen.Naturwissenschaften. 1922; 10: 1041-1049Crossref Scopus (23) Google Scholar was recognized for the catalytic production of ammonia, the precursor to fertilizer. In 1963, the award went to Ziegler4Ziegler K. Natta G. Rosset R. The Nobel Prizes in science.Chem. Nat. 1963; 1963: 503-504Google Scholar and Natta5Natta J. Outlook by Nobel laureates - polymers.Ind. Res. 1968; 10: 66-67Google Scholar for their work on the polymerization of ethylene and propylene, which ushered in the age of plastics. Ten years later, Wilkinson6Wilkinson G. Die Lange Suche nach stabilen alkyl-Ubergangsmetall-Verbindungen (Nobel-Vortrag).Angew. Chem. 1974; 86: 664-667Crossref Google Scholar and Fischer7Fischer E.O. On the way to carbene and carbyne complexes (Nobel lecture).Angew. Chem. 1974; 86: 651-663Crossref Google Scholar were recognized for the groundwork of organometallic chemistry, the sub-discipline that has given us the precision of homogeneous catalysts. In 2001, the Nobel Prize rewarded Knowles,8Knowles W.S. Asymmetric hydrogenations (Nobel lecture).Angew. Chem. Int. Ed. 2002; 41: 1999-2007PubMed Google Scholar Noyori,9Noyori R. Asymmetric catalysis: science and opportunities (Nobel lecture).Angew. Chem. Int. Ed. 2002; 41: 2008-2022Crossref PubMed Scopus (1722) Google Scholar and Sharpless10Sharpless K.B. Searching for new reactivity (Nobel lecture).Angew. Chem. Int. Ed. 2002; 41: 2024-2032Crossref PubMed Scopus (483) Google Scholar for developing stereo-selective catalysts for reduction and oxidation. In 2005, the prize went to Grubbs,11Grubbs R.H. Olefin-metathesis catalysts for the preparation of molecules and materials (Nobel lecture).Angew. Chem. Int. Ed. 2006; 45: 3760-3765Crossref PubMed Scopus (910) Google Scholar Schrock,12Schrock R.R. Multiple metal-carbon bonds for catalytic metathesis reactions (Nobel lecture).Angew. Chem. Int. Ed. 2006; 45: 3748-3759Crossref PubMed Scopus (721) Google Scholar and Chauvin13Chauvin Y. Olefin metathesis: the early days (Nobel lecture).Angew. Chem. Int. Ed. 2006; 45: 3740-3747Crossref PubMed Scopus (440) Google Scholar for the breakthrough of olefin metathesis. Finally, the most recent Nobel Prize in catalysis was awarded in 2010 to Heck, Negishi,14Negishi E.I. Magical power of transition metals: past, present, and future (Nobel lecture).Angew. Chem. Int. Ed. 2011; 50: 6738-6764Crossref PubMed Scopus (514) Google Scholar and Suzuki15Suzuki A. Cross-coupling reactions of organoboranes: an easy way to construct C-C Bonds (Nobel lecture).Angew. Chem. Int. Ed. 2011; 50: 6722-6737Crossref PubMed Scopus (1214) Google Scholar for strategies for C–C bond formation via cross-coupling (Figure 1). The field of catalysis has continued to evolve and broaden. Indeed, in the last 40 years, application of transition-metal chemistry has become mainstream in synthetic organic chemistry laboratories. At the same time, chemists continue to target new transformations, multi-metallic systems, tandem catalysis, photocatalysis, and the reactivity of precisely controlled metal nanoparticles. The current focus of many groups involves strategies designed to make catalysis “green.” Using earth-abundant, less toxic, first-row transition metals, chemists are examining processes known to be particularly environmentally problematic or new avenues to remediation. It is interesting to note that inherent to all of the above advances and research targets is the underlying reliance on the chemistry of transition metals. Be it on a heterogeneous surface or in a designed homogeneous molecule, the ability of transition metals to interact with small molecules has and continues to be exploited for uncovering efficient and transformative chemical production protocols. As we entered the new millennium, non-conventional approaches to catalysis began to emerge from several quarters. Although older work in both organic and inorganic chemistry had shown the possibility of metal-free catalysis, it was in the late 1990s and early 2000s that this notion garnered more serious attention. Such ideas offered an approach to “greener catalysts,” lower costs, and lower toxicity via conceptually distinct protocols. In addition, these new approaches also offered the seductive promise of unprecedented reactivity. In these efforts, three general approaches have emerged over the past two decades. “Organocatalysis” has become a burgeoning field with a range of strategies that exploit small organic molecules to mediate organic transformations.16List B. Introduction: organocatalysis.Chem. Rev. 2007; 107: 5413-5415Crossref Scopus (613) Google Scholar At the same time, “s-block catalysts” have emerged for a range of reactions, including polymerization of alkenes, hydroamination and phosphination reactions, hydrosilylation, hydroboration and hydrogenation catalysis, and enantioselective reductions.17Harder S. Early Main Group Metal Catalysis. Wiley-VCH Verlag, 2020Crossref Scopus (2) Google Scholar The third area of metal-free catalysis is known as “frustrated Lewis pairs” (FLPs). The unique reactivity derived from specific combinations of Lewis acids and bases results from the “frustration” of dative bond formation. It is this area that is the focus of the present discussion. In 2006, the reversible activation of H2 by sterically encumbered phosphines and boranes was reported.18Welch G.C. San Juan R.R.S. Masuda J.D. Stephan D.W. Reversible, metal-free hydrogen activation.Science. 2006; 314: 1124-1126Crossref PubMed Scopus (1331) Google Scholar Although conceptually similar to the work of Piers on B(C6F5)3-mediated hydrosilylation19Parks D.J. Piers W.E. Tris(pentafluorophenyl)boron-catalyzed hydrosilation of aromatic aldehydes, ketones, and esters.J. Am. Chem. Soc. 1996; 118: 9440-9441Crossref Scopus (556) Google Scholar some 10 years before, it was the 2006 finding that garnered more attention and prompted studies targeting metal-free hydrogenation catalysis. In 2007, the first examples of C=N bond reductions were reported.20Chase P.A. Welch G.C. Jurca T. Stephan D.W. Metal-free catalytic hydrogenation.Angew. Chem. Int. Ed. 2007; 46: 8050-8053Crossref PubMed Scopus (469) Google Scholar Since then, the range of substrates has broadened dramatically with landmark findings of metal-free reductions of C=C,21Greb L. Oña-Burgos P. Schirmer B. Grimme S. Stephan D.W. Paradies J. Metal-free catalytic olefin hydrogenations: low-temperature H2-activation by frustrated Lewis pairs.Angew. Chem. Int. Ed. 2012; 51: 10164-10168Crossref PubMed Scopus (179) Google Scholar C=O,22Mahdi T. Stephan D.W. Enabling catalytic ketone hydrogenation by frustrated Lewis pairs.J. Am. Chem. Soc. 2014; 136: 15809-15812Crossref PubMed Scopus (184) Google Scholar,23Scott D.J. Fuchter M.J. Ashley A.E. Nonmetal catalyzed hydrogenation of carbonyl compounds.J. Am. Chem. Soc. 2014; 136: 15813-15816Crossref PubMed Scopus (161) Google Scholar and C≡C24Chernichenko K. Madarász A. Pápai I. Nieger M. Leskelä M. Repo T. A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes.Nat. Chem. 2013; 5: 718-723Crossref PubMed Scopus (245) Google Scholar bonds in addition to other C=N bonds.25Lam J. Szkop K.M. Mosaferi E. Stephan D.W. FLP catalysis: main group hydrogenations of organic unsaturated substrates.Chem. Soc. Rev. 2019; 48: 3592-3612Crossref PubMed Google Scholar Beyond substrate scope, variations of FLP catalysts targeting functional-group tolerance, air stability, and improved reactivity have been explored. Intramolecular and intermolecular FLPs derived from the combination of a variety of Lewis acids and bases have been examined (Figure 2). Effective Lewis acids have been extended to borenium-, carbon-, and phosphorus-based cations.26Weicker S.A. Stephan D.W. Main group Lewis acids in frustrated Lewis pair chemistry: beyond electrophilic boranes.Bull. Chem. Soc. Jpn. 2015; 88: 1003-1016Crossref Scopus (61) Google Scholar Strong Lewis bases such as alkali-metal amides and phosphides have also proved effective, thus demonstrating the generality of the concept. Although the notion of FLP has also been adapted for heterogeneous reductions,27Niu Z. Zhang W. Lan P.C. Aguila B. Ma S. Promoting frustrated Lewis pairs for heterogeneous chemoselective hydrogenation via the tailored pore environment within metal-organic frameworks.Angew. Chem. Int. Ed. 2019; 58: 7420-7424Crossref PubMed Scopus (31) Google Scholar, 28Ghuman K.K. Hoch L.B. Szymanski P. Loh J.Y. Kherani N.P. El-Sayed M.A. Ozin G.A. Singh C.V. Photoexcited surface frustrated Lewis pairs for heterogeneous photocatalytic CO2 reduction.J. Am. Chem. Soc. 2016; 138: 1206-1214Crossref PubMed Scopus (117) Google Scholar, 29Ghoussoub M. Yadav S. Ghuman K.K. Ozin G.A. Singh C.V. Metadynamics-biased ab initio molecular dynamics study of heterogeneous CO2 reduction via surface frustrated Lewis pairs.ACS Catal. 2016; 6: 7109-7117Crossref Scopus (36) Google Scholar perhaps the most elegant advancement has been the modification of FLP catalysts for highly enantioselective hydrogenations of a variety of substrates .30Meng W. Feng X. Du H. Frustrated Lewis pairs catalyzed asymmetric metal-free hydrogenations and hydrosilylations.Acc. Chem. Res. 2018; 51: 191-201Crossref PubMed Scopus (108) Google Scholar The reactivity of FLPs was extended to a growing range of small molecules, prompting a variety of other forms of metal-free catalysis.31Stephan D.W. Erker G. Frustrated Lewis pair chemistry: development and perspectives.Angew. Chem. Int. Ed. 2015; 54: 6400-6441Crossref PubMed Scopus (958) Google Scholar For example, a wide variety of p-block FLPs have been exploited for transfer hydrogenations,32Li S.L. Li G. Meng W. Du H.F. A frustrated Lewis pair catalyzed asymmetric transfer hydrogenation of imines using ammonia borane.J. Am. Chem. Soc. 2016; 138: 12956-12962Crossref PubMed Scopus (86) Google Scholar, 33Stephan D.W. Frustrated Lewis pairs: a new strategy to small molecule activation and hydrogenation catalysis.Dalton Trans. 2009; : 3129-3136Crossref PubMed Scopus (6) Google Scholar, 34Farrell J.M. Heiden Z.M. Stephan D.W. Metal-free transfer hydrogenation catalysis by B(C6F5)3.Organometallics. 2011; 30: 4497-4500Crossref Scopus (74) Google Scholar hydroborations,35Jian Z.B. Kehr G. Daniliuc C.G. Wibbeling B. Erker G. A hydroboration route to geminal P/B frustrated Lewis pairs with a bulky secondary phosphane component and their reaction with carbon dioxide.Dalton Trans. 2017; 46: 11715-11721Crossref PubMed Google Scholar, 36Bamford K.L. Longobardi L.E. Liu L. Grimme S. Stephan D.W. FLP reduction and hydroboration of phenanthrene o-iminoquinones and alpha-diimines.Dalton Trans. 2017; 46: 5308-5319Crossref PubMed Google Scholar, 37Longobardi L.E. Johnstone T.C. Falconer R.L. Russell C.A. Stephan D.W. Hydroboration of phosphaalkynes by HB(C6F5)2.Chem. Eur. J. 2016; 22: 12665-12669Crossref PubMed Scopus (6) Google Scholar, 38Fan X.T. Zheng J.H. Li Z.H. Wang H.D. Organoborane catalyzed regioselective 1,4-hydroboration of pyridines.J. Am. Chem. Soc. 2015; 137: 4916-4919Crossref PubMed Scopus (73) Google Scholar, 39Barnett B.R. Moore C.E. Rheingold A.L. Figueroa J.S. Frustrated Lewis pair behavior of monomeric (boryl)iminomethanes accessed from isocyanide 1,1-hydroboration.Chem. Commun. 2015; 51: 541-544Crossref PubMed Google Scholar, 40Schwendemann S. Fröhlich R. Kehr G. Erker G. Intramolecular frustrated N/B lewis pairs by enamine hydroboration.Chem. Sci. 2011; 2: 1842-1849Crossref Scopus (122) Google Scholar, 41Fleige M. Möbus J. vom Stein T. Glorius F. Stephan D.W. Lewis acid catalysis: catalytic hydroboration of alkynes initiated by Piers' borane.Chem. Commun. 2016; 52: 10830-10833Crossref PubMed Google Scholar C–H borylations,42Rochette É. Desrosiers V. Soltani Y. Fontaine F.G. Isodesmic C-H borylation: perspectives and proof of concept of transfer borylation catalysis.J. Am. Chem. Soc. 2019; 141: 12305-12311Crossref PubMed Scopus (16) Google Scholar, 43Coffinet A. Specklin D. Vendier L. Etienne M. Simonneau A. Frustrated Lewis pair chemistry enables N2 borylation by formal 1,3-addition of a B-H bond in the coordination sphere of tungsten.Chemistry. 2019; 25: 14300-14303Crossref PubMed Scopus (8) Google Scholar, 44Jayaraman A. Misal Castro L.C. Desrosiers V. Fontaine F.G. Metal-free borylative dearomatization of indoles: exploring the divergent reactivity of aminoborane C-H borylation catalysts.Chem. Sci. 2018; 9: 5057-5063Crossref PubMed Google Scholar, 45Légaré M.A. Rochette É. Légaré Lavergne J. Bouchard N. Fontaine F.G. Bench-stable frustrated Lewis pair chemistry: fluoroborate salts as precatalysts for the C-H borylation of heteroarenes.Chem. Commun. 2016; 52: 5387-5390Crossref PubMed Google Scholar, 46Légaré M.A. Courtemanche M.A. Rochette É. Fontaine F.G. BORON CATALYSIS. Metal-free catalytic C-H bond activation and borylation of heteroarenes.Science. 2015; 349: 513-516Crossref PubMed Scopus (233) Google Scholar hydroarylations,47LaFortune J.H.W. Bayne J.M. Johnstone T.C. Fan L. Stephan D.W. Catalytic double hydroarylation of alkynes to 9,9-disubstituted 9,10-dihydroacridine derivatives by an electrophilic phenoxyphosphonium dication.Chem. Commun. 2017; 53: 13312-13315Crossref PubMed Google Scholar, 48Pérez M. Mahdi T. Hounjet L.J. Stephan D.W. Electrophilic phosphonium cations catalyze hydroarylation and hydrothiolation of olefins.Chem. Commun. 2015; 51: 11301-11304Crossref PubMed Google Scholar, 49Guo J. Cheong O. Bamford K.L. Zhou J. Stephan D.W. Frustrated Lewis pair-catalyzed double hydroarylation of alkynes with N-substituted pyrroles.Chem. Commun. 2020; 56: 1855-1858Crossref PubMed Google Scholar and aminations,50Mahdi T. Stephan D.W. Frustrated Lewis pair catalyzed hydroamination of terminal alkynes.Angew. Chem. Int. Ed. 2013; 52: 12418-12421Crossref PubMed Scopus (77) Google Scholar as well as enantioselective α-aminations and Mannich-type reactions.51Shang M. Chan J.Z. Cao M. Chang Y. Wang Q. Cook B. Torker S. Wasa M. C-H functionalization of amines via alkene-derived nucleophiles through cooperative action of chiral and achiral Lewis acid catalysts: applications in enantioselective synthesis.J. Am. Chem. Soc. 2018; 140: 10593-10601Crossref PubMed Scopus (56) Google Scholar, 52Shang M. Wang X.X. Koo S.M. Youn J. Chan J.Z. Yao W.Z. Hastings B.T. Wasa M. Frustrated Lewis acid/Brønsted base catalysts for direct enantioselective alpha-amination of carbonyl compounds.J. Am. Chem. Soc. 2017; 139: 95-98Crossref PubMed Scopus (50) Google Scholar, 53Shang M. Cao M. Wang Q.F. Wasa M. Enantioselective direct Mannich-type reactions catalyzed by frustrated Lewis acid/Brønsted base complexes.Angew. Chem. Int. Ed. 2017; 56: 13338-13341Crossref PubMed Scopus (30) Google Scholar, 54Chan J.Z. Yao W. Hastings B.T. Lok C.K. Wasa M. Direct Mannich-type reactions promoted by frustrated Lewis acid/Brønsted base catalysts.Angew. Chem. Int. Ed. 2016; 55: 13877-13881Crossref PubMed Scopus (30) Google Scholar FLPs have also proved effective catalysts for polymerization55Hong M. Chen J. Chen E.Y. Polymerization of polar monomers mediated by main-group Lewis acid-base pairs.Chem. Rev. 2018; 118: 10551-10616Crossref PubMed Scopus (105) Google Scholar of a variety of acrylates, lactones, cyanamides, vinyl monomers, conjugated polar alkenes, and acrylamide monomers. P(V) and P(III) Lewis acids effect the hydrosilylation of a variety of substrates, as well as the deoxygenation of ketones and the arylation of benzyl fluorides and alkyl and aryl CF3 derivatives.56Bayne J.M. Stephan D.W. C-F bond activation mediated by phosphorus compounds.Chemistry. 2019; 25: 9350-9357Crossref PubMed Scopus (15) Google Scholar The ability of FLPs to stoichiometrically capture CO2 has also evolved to catalytic reductions of CO2 to CO and phosphine oxide, and the catalytic hydroboration of CO2 provides methoxy-boranes, a source of methanol.57Stephan D.W. Erker G. Frustrated Lewis pair chemistry of carbon, nitrogen and sulfur oxides.Chem. Sci. 2014; 5: 2625-2641Crossref Google Scholar In related heterogeneous work, the concept of FLPs has been extended to surface FLPs, in which hydroxylated indium oxide converts CO2 and H2 to CO and H2O.58Ghuman K.K. Wood T.E. Hoch L.B. Mims C.A. Ozin G.A. Singh C.V. Illuminating CO2 reduction on frustrated Lewis pair surfaces: investigating the role of surface hydroxides and oxygen vacancies on nanocrystalline In2O3-x(OH)y.Phys. Chem. Chem. Phys. 2015; 17: 14623-14635Crossref PubMed Google Scholar This wide variety and rapid development of the above applications that have arisen from the remarkably simple concept of FLPs prompts questions about what the future will bring. One way to see the future is to look to the past. Transition-metal-based catalysis was at a similar stage of development in the 1970s–1980s. The substrate scope was broad, and enantioselective catalysis was well established. Nonetheless, the field continued to evolve. New, more selective, and more efficient catalysts achieved the reductions of new, more challenging target substrates. Thus, it seems perhaps trivial to predict that such will also be the case for FLP hydrogenation catalysts. However, there is a distinct difference. Future catalyst technologies are born into an environment where precious-metal-based catalysts are firmly established. Thus, the bar for catalytic activity for known processes is high, as is the cost of process modification or product re-validation. Thus, cheaper catalysts alone are not likely to spawn commercial interest. That being said, FLP catalysis does offer an avenue for low-metal residues, which could be a cost benefit for pharmaceuticals or electronic materials. Another opportunity resides in the potential of heterogenized FLPs. Recent reports have described FLPs deposited in metal-organic frameworks (MOFs). These systems provide substrate-selective catalysts that are also stable and recyclable, features that are certainly cost saving.27Niu Z. Zhang W. Lan P.C. Aguila B. Ma S. Promoting frustrated Lewis pairs for heterogeneous chemoselective hydrogenation via the tailored pore environment within metal-organic frameworks.Angew. Chem. Int. Ed. 2019; 58: 7420-7424Crossref PubMed Scopus (31) Google Scholar,59Niu Z. Bhagya Gunatilleke W.D.C. Sun Q. Lan P.C. Perman J. Ma J.-G. Cheng Y. Aguila B. Ma S. Metal-organic framework anchored with a Lewis pair as a new paradigm for catalysis.Chem. 2018; 4: 2587-2599Abstract Full Text Full Text PDF Scopus (63) Google Scholar Perhaps a richer, more exciting avenue for FLP catalysis lies in the unknown. The ability to activate a wide variety of small molecules suggests possibilities for unrivaled reactivity of substrates traditionally viewed as challenging targets, such as N2, CO, and CH4. For example, no recent main-group paper has garnered more attention than Braunschweig and co-workers’ seminal finding of N2 capture by a B(I) species.60Légaré M.A. Rang M. Bélanger-Chabot G. Schweizer J.I. Krummenacher I. Bertermann R. Arrowsmith M. Holthausen M.C. Braunschweig H. The reductive coupling of dinitrogen.Science. 2019; 363: 1329-1332Crossref PubMed Scopus (89) Google Scholar,61Légaré M.A. Bélanger-Chabot G. Dewhurst R.D. Welz E. Krummenacher I. Engels B. Braunschweig H. Nitrogen fixation and reduction at boron.Science. 2018; 359: 896-900Crossref PubMed Scopus (459) Google Scholar Viewing B(I) as B(III) plus two electrons, it is tempting to speculate that suitably selected FLPs could provide a modular approach to N2 reactivity. This notion is conceptually supported by the activation of H2 by FLPs, which illustrates the separation of electron acceptor and donor components normally engendered at a single metal atom. Similarly, the reactivity of CO or syngas is another avenue that could offer promise for unprecedented metal-free catalysis. In the same fashion, the landmark discovery of FLP-mediated C–H borylations by Fontaine and co-workers46Légaré M.A. Courtemanche M.A. Rochette É. Fontaine F.G. BORON CATALYSIS. Metal-free catalytic C-H bond activation and borylation of heteroarenes.Science. 2015; 349: 513-516Crossref PubMed Scopus (233) Google Scholar suggests that FLPs might also find applications in methane or alkane chemistry. In terms of the lasting impact, FLP chemistry has given us an avenue for metal-free hydrogenation. Commercialization may or may not happen, but this remains largely an economic question rather than a scientific one because catalyst optimization or engineering will be required. The ability to activate small molecules will continue to provide new reactivity and catalysis, although it remains unclear whether new and unrivaled pathways will emerge. Nonetheless, FLP chemistry also provides an avenue for intervening in reactions and trapping species thought to be intermediates.62Szkop K.M. Zhu D.Y. Longobardi L.E. Heck J. Stephan D.W. Interception of intermediates in phosphine oxidation by mesityl nitrile-N-oxide using frustrated Lewis pairs.Dalton Trans. 2018; 47: 8933-8939Crossref PubMed Google Scholar, 63Johnstone T.C. Wee G.N.J.H. Stephan D.W. Accessing frustrated Lewis pair chemistry from a spectroscopically stable and classical Lewis acid-base adduct.Angew. Chem. Int. Ed. 2018; 57: 5881-5884Crossref PubMed Scopus (35) Google Scholar, 64Zhou J.L. Cao L.L. Liu L.L. Stephan D.W. FLP reactivity of [Ph3C]+ and (o-tolyl)3P and the capture of a Staudinger reaction intermediate.Dalton Trans. 2017; 46: 9334-9338Crossref PubMed Google Scholar Alternatively, impact from the concept of FLPs could arise from applications in which FLPs and transition-metal catalysts are used in tandem.65Romero E.A. Zhao T.X. Nakano R. Hu X.B. Wu Y.T. Jazzar R. Bertrand G. Tandem copper hydride-Lewis pair catalysed reduction of carbon dioxide into formate with dihydrogen.Nat. Catal. 2018; 1: 743-747Crossref Scopus (38) Google Scholar Another possibility is the use of FLPs to generate new materials derived from complementary polymers. Cross-linking by substrates could offer potentially new approaches for sensor or photoreactive materials.66Wang M. Nudelman F. Matthes R.R. Shaver M.P. Frustrated Lewis pair polymers as responsive self-healing gels.J. Am. Chem. Soc. 2017; 139: 14232-14236Crossref PubMed Scopus (43) Google Scholar Regardless of the ultimate outcome, perhaps the greatest impact of the advent of FLP chemistry is to focus attention on the relation of steric demands and reactivity well beyond main-group chemistry. For example, the implications of FLP have extended to provide an understanding of the mechanism of small-molecule activation by several enzymatic systems.67Evans R.M. Siritanaratkul B. Megarity C.F. Pandey K. Esterle T.F. Badiani S. Armstrong F.A. The value of enzymes in solar fuels research - efficient electrocatalysts through evolution.Chem. Soc. Rev. 2019; 48: 2039-2052Crossref PubMed Google Scholar, 68Zhang S.G. Appel A.M. Bullock R.M. Reversible heterolytic cleavage of the H-H bond by molybdenum complexes: controlling the dynamics of exchange between proton and hydride.J. Am. Chem. Soc. 2017; 139: 7376-7387Crossref PubMed Scopus (30) Google Scholar, 69Raugei S. Chen S.T. Ho M.H. Ginovska-Pangovska B. Rousseau R.J. Dupuis M. DuBois D.L. Bullock R.M. The role of pendant amines in the breaking and forming of molecular hydrogen catalyzed by nickel complexes.Chemistry. 2012; 18: 6493-6506Crossref PubMed Scopus (92) Google Scholar, 70Bullock J.P. Bond A.M. Boeré R.T. Gietz T.M. Roemmele T.L. Seagrave S.D. Masuda J.D. Parvez M. Synthesis, characterization, and electrochemical studies of PPh(3-n)(dipp)(n) (dipp = 2,6-diisopropylphenyl): steric and electronic effects on the chemical and electrochemical oxidation of a homologous series of triarylphosphines and the reactivities of the corresponding phosphoniumyl radical cations.J. Am. Chem. Soc. 2013; 135: 11205-11215PubMed Google Scholar Of course, FLPs have also brought the reactivity of p-block compounds into the limelight. Attention to the unique utility of p-block species in catalysis continues to encourage inorganic and organic chemists alike not to overlook the utility of p-block species. Indeed, work using p-block compounds in new catalysis is beginning to emerge. For example, a recent insightful and creative work by Cornella and co-workers71Planas O. Wang F. Leutzsch M. Cornella J. Fluorination of arylboronic esters enabled by bismuth redox catalysis.Science. 2020; 367: 313-317Crossref PubMed Scopus (39) Google Scholar exploits a Bi(III)-Bi(V) redox cycle to catalytically fluorinate arenes, a reaction not possible with metal-based catalysts. Looking at main-group chemistry more broadly, much of the published work over the past two decades has demonstrated that the chemistry of p-block species can emulate that of transition metals. Although these analogies are clearly important in giving us a unified picture of reactivity, I believe we are now poised to reach beyond and focus attention on the chemistry where metal catalysts struggle or are inoperative. Certainly, in these efforts, there is a lot that the past century of transition-metal catalysis can teach us, but as the reactivity of p-block systems expands, we should seek out those instances where the chemistry is distinct, unusual, and differentiated from that of metal catalysts. It is such hidden gems in the untapped reactivity of main-group systems that will provide truly innovative catalytic tools and expand the repertoire of the synthetic chemist. The author would like to thank the outstanding undergraduate and graduate students as well as postdoctoral fellows and colleagues who have shared the enthusiasm for developing FLP chemistry. The author is grateful for research support from the Natural Sciences and Engineering Research Council of Canada , being awarded the Canada Research Chair, the 2019 J.C. Polanyi Award, and a 2020 fellowship from the Guggenheim Foundation . Stable Carbenes, Nitrenes, Phosphinidenes, and Borylenes: Past and FutureSoleilhavoup et al.ChemMay 13, 2020In BriefThree decades ago, the first stable carbenes (R2C) were discovered yet remained as laboratory curiosities. Nowadays, a variety of them are known, and their use has spanned across the chemical sciences, including medicinal and material applications. Much less is known about the isolobal group 15 and 13 cousins, but their resemblance to carbenes presages a bright future. Full-Text PDF Open Archive" @default.
• W3033584346 created "2020-06-12" @default.
• W3033584346 creator A5037978366 @default.
• W3033584346 date "2020-07-01" @default.
• W3033584346 modified "2023-10-17" @default.
• W3033584346 title "Catalysis, FLPs, and Beyond" @default.
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