Abstract
While a growing body of literature describes FLP adducts of diamagnetic unsaturated substrates such as alkenes, alkynes and heterocumulenes such as carbon dioxide, capture of the diatomic radical nitric oxide (NO) by intramolecular phosphane/borane FLPs gives a new family of radical frustrated Lewis pair adducts. Capture of NO results in heterocycles with new P-N and B-N bonds featuring a spin density Umpolung of NO to give FLP-NO species that possess significant O-centered radical reactivity. Use of these radical FLP-NO species in C-H functionalization chemistry via H-atom abstraction / radical recombination sequences as well as deployment in nitroxide mediated polymerization of alkenes indicates a rich and diverse chemistry for FLP-NO species. An alternative, complementary strategy to generate radical FLPs involves the use of transition metal centers with unpaired electrons as the Lewis acid component of an FLP in conjunction with a tethered but hindered Lewis base.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Kenward AL, Piers WE (2008) Heterolytic H2 activation by nonmetals. Angew Chem Int Ed 47:38–41
Stephan DW, Erker G (2010) Frustrated Lewis pairs: metal-free hydrogen activation and more. Angew Chem Int Ed 49:46–76
Erker G (2011) Frustrated Lewis pairs: reactions with dihydrogen and other “small molecules”. C R Chim 14:831–841
Stephan DW (2012) Discovery of frustrated Lewis pairs: intermolecular FLPs for activation of small molecules. Top Curr Chem. doi:10.1007/128_2012_381
Kehr G, Schwendemann S, Erker G (2012) Intramolecular frustrated Lewis pairs: formation and chemical features. Top Curr Chem. doi: 10.1007/128_2012_373
Grimme S, Kruse H, Goerigk L, Erker G (2010) The mechanism of dihydrogen activation by frustrated Lewis pairs revisited. Angew Chem Int Ed 49:1402–1405
Rokob TA, Hamza A, Stirling A, Soós T, Pápai I (2008) Turning frustration into bond activation: a theoretical mechanistic study on heterolytic hydrogen splitting by frustrated Lewis pairs. Angew Chem Int Ed 47:2435–2438
Welch GC, Stephan DW (2007) Facile heterolytic cleavage of dihydrogen by phosphines and boranes. J Am Chem Soc 129:1880–1881
McCahill JSJ, Welch GC, Stephan DW (2007) Reactivity of “frustrated Lewis pairs”: three-component reactions of phosphines, a borane, and olefins. Angew Chem Int Ed 46:4968–4971
Mömming CM, Otten E, Kehr G, Fröhlich R, Grimme S, Stephan DW, Erker G (2009) Reversible metal-free carbon dioxide binding by frustrated Lewis pairs. Angew Chem Int Ed 48:6643–6646
Dureen MA, Stephan DW (2010) Reactions of boron amidinates with CO2 and CO and other small molecules. J Am Chem Soc 132:13559–13568
Otten E, Neu RC, Stephan DW (2009) Complexation of nitrous oxide by frustrated Lewis pairs. J Am Chem Soc 131:9918–9919
Neu RC, Otten E, Lough A, Stephan DW (2011) The synthesis and exchange chemistry of frustrated Lewis pair-nitrous oxide complexes. Chem Sci 2:170–176
Mömming CM, Kehr G, Wibbeling B, Fröhlich R, Erker G (2010) Addition reactions to the intramolecular mesityl2P-CH2-CH2-B(C6F5)2 frustrated Lewis pair. Dalton Trans 39:7556–7564
Hicks RG (2010) Stable radicals: fundamentals and applied aspects of odd-electron compounds. Wiley, Chichester
Hartung J (2009) Organic radical reactions associated with nitrogen monoxide. Chem Rev 109:4500–4517
Richter-Addo GB, Legzdins P (1992) Metal nitrosyls. Oxford University Press, New York
Hayton TW, Legzdins P, Sharp WB (2002) Coordination and organometallic chemistry of metal-NO complexes. Chem Rev 102:935–992
Becker PN, Bergman RG (1983) Reversible exchange of (η5-cyclopentadienyl)(dinitrosoalkane)cobalt complexes with alkenes. Kinetic and spectroscopic evidence for cyclopentadienyldinitrosylcobalt as a reactive intermediate. J Am Chem Soc 105:2985–2995
Becker PN, Bergman RG (1983) A transition-metal-based method for 1,2-diamination of alkenes. Synthesis of cobalt dinitrosoalkanes from alkenes, nitric oxide, and (η5-cyclopentadienyl)(nitrosyl)cobalt dimer and their reduction to primary vicinal diamines. Organometallics 2:787–796
Becker PN, White MA, Bergman RG (1980) A new method for 1,2-diamination of alkenes using cyclopentadienylnitrosylcobalt dimer/NO/LiAlH4. J Am Chem Soc 102:5676–5677
Schomaker JM, Boyd WC, Stewart IC, Toste FD, Bergman RG (2008) Cobalt dinitrosoalkane complexes in the C-H functionalization of olefins. J Am Chem Soc 130:3777–3779
Boyd WC, Crimmin MR, Rosebrugh LE, Schomaker JM, Bergman RG, Toste FD (2010) Cobalt-mediated, enantioselective synthesis of C(2) and C(1) dienes. J Am Chem Soc 132:16365–16367
Ignarro LJ (2010) Nitric oxide, biology and pathobiology, 2nd edn. Academic, San Diego
Kerwin JF Jr, Lancaster JR Jr, Feldman PL (1995) Nitric oxide: a new paradigm for second messengers. J Med Chem 38:4343–4362
Riccio DA, Schoenfisch MH (2012) Nitric oxide release: part I. Macromolecular scaffolds. Chem Soc Rev 41:3731–3741
Sortino S (2010) Light-controlled nitric oxide delivering molecular assemblies. Chem Soc Rev 39:2903–2913
Hwang S, Cha W, Meyeroff ME (2006) Polymethacrylates with a covalently linked CuII-cyclen complex for the in situ generation of nitric oxide from nitrosothiols in blood. Angew Chem Int Ed 45:2745–2748
Oh BK, Meyeroff ME (2003) Spontaneous catalytic generation of nitric oxide from S-nitrosothiols at the surface of polymer films doped with lipophilic copper(II) complex. J Am Chem Soc 125:9552–9553
Carpenter AW, Schoenfisch MH (2012) Nitric oxide release: part II. Therapeutic applications. Chem Soc Rev 41:3742–3752
Lee J, Chen L, West AH, Richeter-Addo GB (2002) Interactions of organic nitroso compounds with metals. Chem Rev 102:1019–1066
Gowenlock BG, Richter-Addo GB (2004) Preparations of C-nitroso compounds. Chem Rev 104:3315–3340
Luo Y-R (2002) Handbook of bond dissociation energies in organic compounds. CRC, Boca Raton
Rathore R, Kochi JK (1998) Cofacial phenylene donors as novel organic sensors for the reversible binding of nitric oxide. J Org Chem 63:8630–8631
Rathore R, Lindeman SV, Rao KSSP, Sun D, Kochi JK (2000) Guest penetration deep within the cavity of calix[4]arene hosts: the tight binding of nitric oxide to distal (cofacial) aromatic groups. Angew Chem Int Ed 39:2123–2127
Rathore R, Lindeman SV, Kochi JK (1998) An efficient Venus flytrap for the reversible binding of nitric oxide. Angew Chem Int Ed 37:1585–1587
Korth H-G, Ingold KU, Sustmann R, de Groot H, Sies H (1992) Tetramethyl-ortho-quinodimethane, first member of a family of custom-tailored chelatropic spin traps for nitric oxide. Angew Chem Int Ed 31:891–893
Tebben L, Studer A (2011) Nitroxides: applications in synthesis and in polymer chemistry. Angew Chem Int Ed 50:5034–5068, and references herein
Likhtenshtein G, Yamauchi J, Nakatsuji S, Smirnov AI, Tamura R (2008) Nitroxides: applications in chemistry, biomedicine, and materials science. Wiley-VCH, Weinhem
Kuhn LP, Doali JO, Wellman C (1960) The reaction of nitric oxide with triethyl phosphite. J Am Chem Soc 82:4792–4794
Longhi R, Ragsdale RO, Drago RS (1962) Reactions of nitrogen(II) oxide with miscellaneous Lewis bases. Inorg Chem 1:768–770
Lim MD, Lorkovic IM, Ford PC (2002) Kinetics of the oxidation of triphenylphosphine by nitric oxide. Inorg Chem 41:1026–1028
Zhao Y-L, Bartberger MD, Goto K, Shimada K, Kawashima T, Houk KN (2004) Theoretical evidence for enhanced NO dimerization in aromatic hosts: implications for the role of the electrophile (NO)2 in nitric oxide chemistry. J Am Chem Soc 126:7964–7965
Bakac A, Schouten M, Johnson A, Song W, Pestovsky O, Szajna-Fuller W (2009) Oxidation of a water-soluble phosphine and some spectroscopic probes with nitric oxide and nitrous acid in aqueous solutions. Inorg Chem 48:6979–6985
Ray AB (1967) Reactions of boron trifluoride with oxides of nitrogen. Inorg Chem 6:110–113
Brownstein S, Irish B (1988) Charge-transfer complexes of nitric oxide, tri or tetravalent halides and aromatic hydrocarbons. Polyhedron 7:97–101
Novick SE, Davies PB, Dyke TR, Klemperer W (1973) Polarity of van der Waals molecules. J Am Chem Soc 95:8547–8550
Cardenas AJP, Culotta BJ, Warren TH, Grimme S, Stute A, Fröhlich R, Kehr G, Erker G (2011) Capture of NO by a frustrated Lewis pair: a new type of persistent N-oxyl radical. Angew Chem Int Ed 50:7567–7571
Spies P, Erker G, Kehr G, Bergander K, Fröhlich R, Grimme S, Stephan DW (2007) Rapid intramolecular heterolytic dihydrogen activation starting from a four-membered heterocyclic phosphane-borane adduct. Chem Commun 5072–5074
Spies P, Schwendemann S, Lange S, Kehr G, Fröhlich R, Erker G (2008) Metal-free catalytic hydrogenation of enamines, imines, and conjugated phosphinoalkenylboranes. Angew Chem Int Ed 47:7543–7546
Spies P, Kehr G, Bergander K, Wibbeling B, Fröhlich R, Erker G (2009) Metal-free dihydrogen activation chemistry: structural and dynamic features of intramolecular P/B pairs. Dalton Trans 1534–1541
Nichols NL, Hause CD, Noble RH (1955) Near infrared spectrum of nitric oxide. J Chem Phys 23:57–61
Yonekuta Y, Oyaizu K, Nishide H (2007) Structural implication of oxoammonium cations for reversible organic one-electron redox reaction to nitroxide radicals. Chem Lett 36:866–867
Talsi EP, Semikolenova NV, Panchenko VN, Sobolev AP, Babushkin DE, Shubin AA, Zakharov VA (1999) The metallocene/methylaluminoxane catalysts formation: ESR spin probe study of Lewis acidic sites of methlyalumoxane. J Mol Catal A 139:131–137
Knauer BR, Napier JJ (1976) The nitroxide hyperfine splitting constant of the nitroxide functional group as a solvent polarity parameter. The relative importance for a solvent polarity parameter of its being a cybotactic probe vs. its being a model process. J Am Chem Soc 98:4395–4400
Wu A, Mader EA, Datta A, Hrovat DA, Bordon WT, Mayer JM (2009) Nitroxyl radical plus hydroxylamine pseudo self-exchange reactions: tunneling in hydrogen atom transfer. J Am Chem Soc 131:11985–11997
Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104
Grimme S, Ehrlich S, Goerigk L (2011) Effect of the damping function in dispersion corrected density functional theory. J Comput Chem 32: 1456–1465
Staroverov VN, Scuseria GE, Tao J, Perdew JP (2003) Comparative assessment of a new nonempirical density functional: molecules and hydrogen-bonded complexes. J Chem Phys 119:12129
Weigend F, Ahlrichs R (2005) Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys Chem Chem Phys 7:3297
Grimme S (2006) Semiempirical hybrid density functional with perturbative second-order correlation. J Chem Phys 124:034108
Warren JJ, Tronic TA, Mayer JM (2010) Thermochemistry of proton-coupled electron transfer reagents and its implications. Chem Rev 110:6961–7001
Fukuto JM, Bartberger MD, Dutton AS, Paolocci N, Wink DA, Houk KN (2005) The physiological chemistry and biological activity of nitroxyl (HNO): the neglected, misunderstood, and enigmatic nitrogen oxide. Chem Res Toxicol 18:790–801
Irvine HC, Ritchie RH, Favaloro JL, Andrews KL, Widdop RE, Kemp-Harper BK (2008) Nitroxyl (HNO): the Cinderella of the nitric oxide story. Trends Pharmacol Sci 29:601–608
Paolocci N, Jackson MI, Lopez BE, Miranda K, Tocchetti CG, Wink DA, Hobbs AJ, Fukuto JM (2007) The pharmacology of nitroxyl (HNO) and its therapeutic potential: not just the Janus face of NO. Pharmacol Ther 113:442–458
Connolly TJ, Scaiano JC (1997) Reactions of the “stable” nitroxide radical TEMPO. Relavance to "living" free radical polymerizations and autopolymerization of styrene. Tetrahedron Lett 38:1133–1136
Babiarz JE, Cunkle GT, DeBellis AD, Eveland D, Pastor SD, Shum SP (2002) The thermal reaction of sterically hindered nitroxyl radicals with allylic and benzylic substrates: experimental and computational evidence for divergent mechanisms. J Org Chem 67:6831–6834
Sajid M, Stute A, Cardenas AJP, Culotta BJ, Hepperle JAM, Warren TH, Schirmer B, Grimme S, Studer A, Daniliuc CG, Fröhlich R, Petersen JL, Kehr G, Erker G (2012) N,N-Addition of frustrated Lewis pairs to nitric oxide: an easy entry to a unique family of aminoxyl radicals. J Am Chem Soc 134:10156–10168
Gao H, Ohno S, Matyjaszewski K (2006) Low polydispersity star polymers via cross-linking macromonomers by ATRP. J Am Chem Soc 128:15111–15113
Matyjaszewski K (2000) Controlled/living radical polymerization progress in ATRP, NMP, and RAFT. Am Chem Soc, Washington, DC
Matyjaszewski K, Woodworth BE, Zhang X, Gaynor SG, Metzner Z (1998) Simple and efficient synthesis of various alkoxyamines for stable free radical polymerization. Macromolecules 31:5955–5957
Wass DF, Chapman AM (2012) Frustrated Lewis Pairs Beyond the Main Group: Transition Metal-Containing Systems. Top Curr Chem DOI : 10.1007/128_2012_395
Chapman AM, Haddow MF, Wass DF (2011) Frustrated Lewis pairs beyond the main group: cationic zirconocene phosphinoaryloxide complexes and their application in catalytic dehydrogenation of amine boranes. J Am Chem Soc 133:8826–8829
Chapman AM, Haddow MF, Wass DF (2011) Frustrated Lewis pairs beyond the main group: synthesis, reactivity, and small molecule activation with cationic zirconocene phosphinoaryloxide complexes. J Am Chem Soc 133:18463–18478
Chapman AM, Wass DF (2012) Cationic Ti(IV) and neutral Ti(III) titanocene–phosphinoaryloxide frustrated Lewis pairs: hydrogen activation and catalytic amine-borane dehydrogenation. Dalton Trans 9067–9072
Willoughby CA, Duff RR Jr, Davis WM, Buchwald SL (1996) Preparation of novel titanium complexes bearing o-phosphinophenol ligands. Organometallics 15:472–475
Schulz F, Sumerin V, Heikkinen S, Pedersen B, Wang C, Atsumi M, Leskelä M, Repo T, Pyykkö P, Petry W, Rieger B (2011) Molecular hydrogen tweezers: structure and mechanisms by neutron diffraction, NMR, and deuterium labeling studies in solid and solution. J Am Chem Soc 133:20245–20257
Voss T, Mahdi T, Otten E, Fröhlich R, Kehr G, Stephan DW, Erker G (2012) Frustrated Lewis pair behavior of intermolecular amine/B(C6F5)3 pairs. Organometallics 31:2367–2378
Acknowledgments
The authors warmly thank their coworkers and collaborating research groups for their valuable contributions to the work described in this article. T.H.W is grateful to the US National Science Foundation (CHE-0840453 and CHE-0957606) as well as the Petroleum Research Fund (51971-ND3) for financial support. G.E. thanks the Deutsche Forschungsgemeinschaft, the Fond der Chemischen Industrie, the Alexander von Humboldt-Stiftung and the European Research Council for financial support.
Author information
Authors and Affiliations
Corresponding authors
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2013 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Warren, T.H., Erker, G. (2013). Radical Frustrated Lewis Pairs. 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_390
Download citation
DOI: https://doi.org/10.1007/128_2012_390
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)