Keywords
- σ Bond metathesis
- Bifunctional catalysis
- C–H activation
- Double H transfer
- Double H transfer cascade
- Frustrated Lewis pair
- H2 activation
- Hydrogenation
- Meerwein–Pondorf–Verley reduction
- Metal-free hydrogenation
- Transfer hydrogenation
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
Welch GC, Juan RRS, Masuda JD, Stephan DW (2006) Reversible, metal-free hydrogen activation. Science 314(5802):1124
Grimme S, Kruse H, Goerigk L, Erker G (2010) The mechanism of dihydrogen activation by frustrated Lewis pairs revisited. Angew Chem Int Ed 49(8):1402
Stephan DW, Erker G (2010) Frustrated Lewis pairs: metal-free hydrogen activation and more. Angew Chem Int Ed 49(1):46
Jiang C, Blacque O, Berke H (2009) Metal-free hydrogen activation and hydrogenation of imines by 1,8-bis(dipentafluorophenylboryl)naphthalene. Chem Commun 37:5518
Jiang C, Blacque O, Berke H (2009) Metal-free hydrogen activation by the frustrated Lewis pairs of CIB(C6F5)2 and HB(C6F5)2 and bulky Lewis bases. Organometallics 28:5233
Jiang C, Blacque O, Fox T, Berke H (2011) Reversible, metal-free hydrogen activation by frustrated Lewis pairs. Dalton Trans 40:1091
Jiang C, Blacque O, Fox T, Berke H (2011) Heterolytic cleavage of H2 by frustrated B/N Lewis pairs. Organomet 30:2117
Hamilton CW, Baker RT, Staubitz A, Manners I (2009) B-N compounds for chemical hydrogen storage. Chem Soc Rev 38(1):279
Labinger JA, Bercaw JE (2002) Understanding and exploiting C-H bond activation. Nature 417(6888):507
Watson PL (1983) Methane exchange-reactions of lanthanide and early-transition-metal methyl complexes. J Am Chem Soc 105(21):6491
Thompson ME, Baxter SM, Bulls R, Burger BJ, Nolan MC, Santsiero BD, Schaefer WP, Bercaw JE (1987) Alpha-bond metathesis for C-H bonds of hydrocarbons and Sc-H, Sc-alyl, Sc-aryl bonds of permethylscandocene derivatives – evidence for noninvolvement of the pi-system in electrophilic activation of aromatic and vinylic C-H bonds. J Am Chem Soc 109(1):203
Steigerwald ML, Goddard WA (1984) 2s + 2s reactions at transition-metals. 1. The reactions of D2 with Cl2TiH+, Cl2TiH+, and Cl2ScH. J Am Chem Soc 106(2):308
Cundari TR (1992) Methane activation by group-IVB imido complexes. J Am Chem Soc 114(26):10557
Cummins CC, Baxter SM, Wolczanski PT (1988) Methane and benzene activation via transient (tert-Bu3SiNH)2Zr═NSi-tert-Bu3. J Am Chem Soc 110(26):8731
Noyori R, Ohkuma T (2001) Asymmetric catalysis by architectural and functional molecular engineering: practical chemo- and stereoselective hydrogenation of ketones. Angew Chem Int Ed 40(1):40
Chakraborty S, Blacque O, Fox T, Berke H (2012) Cheap metals for nobel tasks: synthesis and catalytic activity of molybdenum and tungsten nitrosyl hydride complexes bearing a triphosphine chelate ligand (submitted)
Cui W, Li S, Wayland BB (2007) Factors contributing to one-electron metalloradical activation of ethene and carbon monoxide illustrated by reactions of Co(II), Rh(II), and Ir(II) porphyrins. J Organomet Chem 692(15):3198
Zhang XX, Parks GF, Wayland BB (1997) One-electron activation of CO by a rhodium(II) porphyrin bimetalloradical complex and concerted reactions of two (RhCO) units. J Am Chem Soc 119(34):7938
Wayland BB, Ba SJ, Sherry AE (1992) Reactions of H2(D2) with rhodium(II) metalloradical – kinetic evidence for a 4-centered transition-state. Inorg Chem 31(1):148
Spies P, Frohlich R, Kehr G, Erker G, Grimme S (2008) Structural importance of secondary interactions in molecules: origin of unconventional conformations of phosphine-borane adducts. Chem A Eur J 14(3):779
Spies P, Schwendemann S, Lange S, Kehr G, Frohlich R, Erker G (2008) Metal-free catalytic hydrogenation of enamines, imines, and conjugated phosphinoalkenylboranes. Angew Chem Int Ed 47(39):7543
Mahdi T, Heiden ZM, Grimme S, Stephan DW (2012) Metal-free aromatic hydrogenation: aniline to cyclohexyl-amine derivatives. J Am Chem Soc 134(9):4088
Lindqvist M, Sarnela N, Sumerin V, Chernichenko K, Leskelae M, Repo T (2012) Heterolytic dihydrogen activation by B(C6F5)3 and carbonyl compounds. Dalton Trans 41(15):4310
Sumerin V, Schulz F, Nieger M, Leskela M, Repo T, Rieger B (2008) Facile heterolytic H2 activation by amines and B(C6F5)3. Angew Chem Int Ed 47(32):6001
Sumerin V, Chernichenko K, Nieger M, Leskelae M, Rieger B, Repo T (2011) Highly active metal-free catalysts for hydrogenation of unsaturated nitrogen-containing compounds. Adv Synth Catal 353(11–12):2093
Sumerin V, Schulz F, Atsumi M, Wang C, Nieger M, Leskela M, Repo T, Pyykko P, Rieger B (2008) Molecular tweezers for hydrogen: synthesis, characterization, and reactivity. J Am Chem Soc 130(43):14117
Berke H (2010) Conceptual approach to the reactivity of dihydrogen. Chemphyschem 11(9):1837
Fernandez I, Sierra MA, Cossio FP (2007) In-plane aromaticity in double group transfer reactions. J Org Chem 72(4):1488
Fernandez I, Bickelhaupt FM, Cossio FP (2012) Type-I dyotropic reactions: understanding trends in barriers. Chem Eur J 18(39):12517
Arrieta A, de Cozar A, Cossio FP (2011) Cyclic electron delocalization in pericyclic reactions. Curr Org Chem 15(20):3594
Robertson APM, Leitao EM, Manners I (2011) Catalytic redistribution and polymerization of diborazanes: unexpected observation of metal-free hydrogen transfer between aminoboranes and amine-boranes. J Am Chem Soc 133(48):19322
Leitao EM, Stubbs NE, Robertson APM, Helten H, Cox RJ, Lloyd-Jones GC, Manners I (2012) Mechanism of metal-free hydrogen transfer between amine–boranes and aminoboranes. J Am Chem Soc 134(40):16805–16816
Node M, Kajimoto T, Ozeki M (2010) Development of novel asymmetric reactions and their application to the synthesis of natural products. Heterocycles 81(5):1061
Budzelaar PHM, Talarico G (2003) Struct Bond (Berlin Germany) 105(Group13, Chemistry III):141
Doering WV, Young RW (1950) Partially asymmetric Meerwein–Ponndorf–Verley reactions. J Am Chem Soc 72(1):631
Yang X, Zhao L, Fox T, Wang Z-X, Berke H (2010) Transfer hydrogenation of imines with ammonia-borane: a concerted double-hydrogen-transfer reaction. Angew Chem Int Ed 49(11): 2058
Yang X, Fox T, Berke H (2012) Synthetic and mechanistic studies of metal-free transfer hydrogenations applying polarized olefins as hydrogen acceptors and amine borane adducts as hydrogen donors. Org Biomol Chem 10(4):852
Yang X, Fox T, Berke H (2011) Facile metal free regioselective transfer hydrogenation of polarized olefins with ammonia borane. Chem Commun 47(7):2053
Yang X, Fox T, Berke H (2011) Ammonia borane as a metal free reductant for ketones and aldehydes: a mechanistic study. Tetrahedron 67(37):7121
Pons V, Baker RT, Szymczak NK, Heldebrandt DJ, Linehan JC, Matus MH, Grant DJ, Dixon DA (2008) Coordination of aminoborane, NH2BH2, dictates selectivity and extent of H2 release in metal-catalysed ammonia borane dehydrogenation. Chem Commun (48):6597
Shvo Y, Czarkie D, Rahamim Y, Chodosh DF (1986) A new group of ruthenium complexes – structure and catalysis. J Am Chem Soc 108(23):7400
Blum Y, Czarkie D, Rahamim Y, Shvo Y (1985) (Cyclopentadienone)ruthenium carbonyl complexes – a new class of homogeneous hydrogenation catalysts. Organometallics 4(8):1459
Comas-Vives A, Ujaque G, Lledos A (2007) Hydrogen transfer to ketones catalyzed by Shvo’s ruthenium hydride complex: a mechanistic insight. Organometallics 26:4135
Conley BL, Pennington-Boggio MK, Boz E, Williams TJ (2010) Discovery, applications, and catalytic mechanisms of Shvo’s catalyst. Chem Rev 110(4):2294
Casey CP, Singer SW, Powell DR, Hayashi RK, Kavana M (2001) Hydrogen transfer to carbonyls and imines from a hydroxycyclopentadienyl ruthenium hydride: evidence for concerted hydride and proton transfer. J Am Chem Soc 123(6):1090
Casey CP, Strotman NA, Beetner SE, Johnson JB, Priebe DC, Vos TE, Khodavandi B, Guzei IA (2006) The PPh3-substituted hydroxycyclopentadienyl ruthenium hydride 2,5-Ph-2-3,4-tol(2)(eta(5)-C4COH) Ru(CO)(PPh3)H is a more efficient catalyst for hydrogenation of aldehydes. Organometallics 25(5):1230
Noyori R, Hashiguchi S (1997) Asymmetric transfer hydrogenation catalyzed by chiral ruthenium complexes. Acc Chem Res 30:97
Clapman SE, Hazdovic A, Morris RH (2004) Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes. Coord Chem Rev 248:2201
Gunanathan C, Milstein D (2011) Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and “green” catalysis. Acc Chem Res 44(8):588
Ikariya T (2011) Bifunctional transition metal-based molecular catalysts for asymmetric syntheses. Top Organomet Chem 37:31
Ikariya T (2011) Chemistry of concerto molecular catalysis based on the metal/NH bifunctionality. Bull Chem Soc Jpn 84(1):1
Ikariya T, Blacker AJ (2007) Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular. Acc Chem Res 40(12):1300
Ikariya T, Murata K, Noyori R (2006) Bifunctional transition metal-based molecular catalysts for asymmetric syntheses. Org Biomol Chem 4:393
Landwehr A, Dudle B, Fox T, Blacque O, Berke H (2012) Bifunctional rhenium complexes for the catalytic transfer-hydrogenation reactions of ketones and imines. Chem Eur J 18(18):5701
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Additional information
Dedicated to Nobel Laureate Roald Hoffmann on the occasion of his 75th birthday
Rights and permissions
Copyright information
© 2013 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Berke, H., Jiang, Y., Yang, X., Jiang, C., Chakraborty, S., Landwehr, A. (2013). Coexistence of Lewis Acid and Base Functions: A Generalized View of the Frustrated Lewis Pair Concept with Novel Implications for Reactivity. In: Erker, G., Stephan, D. (eds) Frustrated Lewis Pairs II. Topics in Current Chemistry, vol 334. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2012_400
Download citation
DOI: https://doi.org/10.1007/128_2012_400
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-37758-7
Online ISBN: 978-3-642-37759-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)