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Novel Al-Based FLP Systems

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Frustrated Lewis Pairs II

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 334))

Abstract

Al/P based frustrated Lewis pairs (FLPs) having coordinatively unsaturated aluminium and phosphorus atoms in a single molecule were obtained on a multigram scale by hydroalumination of alkynylphosphines. Steric shielding prevented the formation of adducts and the quenching of the conflicting Lewis acidic and basic functionalities. These FLPs reacted with terminal alkynes by C–H bond cleavage with the protons bonded to phosphorus and the alkynido groups coordinated to aluminium. Alternatively, a five-membered heterocycle was formed by C≡C triple bond activation. Similar heterocycles resulted from the reversible coordination of carbon dioxide. Particularly interesting is their unique propensity to react as effective ion pair receptors for the complexation of alkali metal hydrides and their capability to activate such ionic hydrides as phase transfer catalysts. Sterically less shielded compounds gave dimers via Al–P interactions. These compounds are still active as masked FLPs and form complexes with carbon dioxide or phenyl isocyanate. Alternative routes gave methylene bridged Al–P compounds which were also shown to coordinate CO2. Bimolecular systems exhibit similar properties. They activate terminal alkynes and isobutene or reduce CO2 to methanol and carbon monoxide. Hydroalumination of ynamines proved to be an excellent method for the generation of Al/N based Lewis pairs. These compounds were shown to activate phenylethyne reversibly or to undergo insertion reactions with carbodiimide. The constitution of the latter products is determined by cooperative interactions between aluminium and nitrogen.

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Abbreviations

3c-2e:

Three centre-two electron

DFT:

Density functional theory

Et:

Ethyl

FLP:

Frustrated Lewis pair

J :

Coupling constant

Me:

Methyl

Mes:

Mesityl, 2,4,6-trimethylphenyl

min:

Minutes

r.t.:

Room temperature

THF:

Tetrahydrofuran

References

  1. Welch GC, Juan RRS, Masuda JD, Stephan DW (2006) Reversible, metal-free hydrogen activation. Science 314:1124–1126

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. Otten E, Neu RC, Stephan DW (2009) Complexation of nitrous oxide by frustrated Lewis pairs. J Am Chem Soc 131:9918–9919

    Article  CAS  Google Scholar 

  4. Neu RC, Otten E, Stephan DW (2009) Bridging binding modes of phosphine-stabilized nitrous oxide to Zn(C6F5)2. Angew Chem Int Ed 48:9709–9712

    Article  CAS  Google Scholar 

  5. 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

    Article  CAS  Google Scholar 

  6. Chase AC, Jurca T, Stephan DW (2008) Lewis acid-catalyzed hydrogenation of imines and nitriles with H2. Chem Commun 1701–1703

    Google Scholar 

  7. Chen D, Klankermayer J (2008) Metal-free catalytic hydrogenation with tris(perfluorophenyl)borane. Chem Commun 2130–2131

    Google Scholar 

  8. 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

    Article  CAS  Google Scholar 

  9. Axenov KV, Kehr G, Fröhlich R, Erker G (2009) Catalytic hydrogenation of sensitive organometallic compounds by antagonistic N/B Lewis pair catalyst systems. J Am Chem Soc 131:3454–3455

    Article  CAS  Google Scholar 

  10. Wang H, Fröhlich R, Kehr G, Erker G (2008) Heterolytic dihydrogen activation with the 1,8-bis(diphenylphosphino)naphthalene/B(C6F5)3 pair and its application for metal-free catalytic hydrogenation of silyl enol ethers. Chem Commun 5966–5968

    Google Scholar 

  11. Dureen MA, Brown CC, Stephan DW (2010) Deprotonation and addition reactions of frustrated Lewis pairs with alkynes. Organometallics 29:6594–6607

    Article  CAS  Google Scholar 

  12. Sumerin V, Schulz F, Nieger M, Leskelä M, Repo T, Rieger B (2008) Facile heterolytic H2 activation by amines and B(C6F5)3. Angew Chem Int Ed 47:6001–6003

    Article  CAS  Google Scholar 

  13. Sumerin V, Schulz F, Atsumi M, Wang C, Nieger M, Leskelä M, Repo T, Pyykkö P, Rieger B (2008) Molecular tweezers for hydrogen: synthesis, characterisation and reactivity. J Am Chem Soc 130:14117–14119

    Article  CAS  Google Scholar 

  14. Geier SJ, Stephan DW (2009) Lutidine/B(C6F5)3: at the boundary of classical and frustrated Lewis pair reactivity. J Am Chem Soc 131:3476–3477

    Article  CAS  Google Scholar 

  15. Geier SJ, Gille AL, Gilbert TM, Stephan DW (2009) From classical adducts to frustrated Lewis pairs: steric effects in the interactions of pyridines and B(C6F5)3. Inorg Chem 48:10466–10474

    Article  CAS  Google Scholar 

  16. Erös G, Mehdi H, Pápai I, Rokob TA, Király P, Tárkányi G, Soós T (2010) Expanding the scope of metal-free catalytic hydrogenation through frustrated Lewis pair design. Angew Chem Int Ed 49:6559–6563

    Article  Google Scholar 

  17. Geier SJ, Chase PA, Stephan DW (2010) Metal-free reductions of N-heterocycles via Lewis acid catalyzed hydrogenation. Chem Commun 4884–4886

    Google Scholar 

  18. Chase PA, Welch GC, Jurca T, Stephan DW (2007) Metal-free catalytic hydrogenation. Angew Chem Int Ed 46:8050–8053

    Article  CAS  Google Scholar 

  19. Dureen MA, Brown CC, Stephan DW (2010) Addition of enamines or pyrroles and B(C6F5)3 “frustrated Lewis pairs” to alkynes. Organometallics 29:6422–6432

    Article  CAS  Google Scholar 

  20. Holschumacher D, Bannenberg T, Hrib CG, Jones PG, Tamm M (2008) Heterolytic dihydrogen activation by a frustrated carbene-borane Lewis pair. Angew Chem Int Ed 47:7428–7432

    Article  CAS  Google Scholar 

  21. Chase PA, Stephan DW (2008) Hydrogen and amine activation by a frustrated Lewis pair of a bulky N-heterocyclic carbene and B(C6F5)3. Angew Chem Int Ed 47:7433–7437

    Article  CAS  Google Scholar 

  22. Alcarazo M, Gomez C, Holle S, Goddard R (2010) Exploring the reactivity of carbon(0)/borane-based frustrated Lewis pairs. Angew Chem Int Ed 49:5788–5791

    Article  CAS  Google Scholar 

  23. 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

    Article  CAS  Google Scholar 

  24. Uhl W (2008) Hydroalumination and hydrogallation of alkynes: new insights into the course of well-known reactions. Coord Chem Rev 252:1540–1563

    Article  CAS  Google Scholar 

  25. Appelt C, Westenberg H, Bertini F, Ehlers AW, Slootweg JC, Lammertsma K, Uhl W (2011) Geminal phosphorus/aluminium-based frustrated Lewis pairs: C–H versus C≡C activation and CO2 fixation. Angew Chem Int Ed 50:3925–3928

    Article  CAS  Google Scholar 

  26. Uhl W, Bock HR, Claesener M, Layh M, Tiesmeyer I, Würthwein EU (2008) cis/trans-Isomerism of hydroalumination and hydrogallation products – reflections on stability and rearrangement mechanism. Chem Eur J 14:11557–11564

    Article  CAS  Google Scholar 

  27. Appelt C, Slootweg JC, Lammertsma K, Uhl W (2012) A phosphorus/aluminum-based frustrated Lewis pair as ion pair receptor: alkali metal hydride adducts and phase-transfer catalysis. Angew Chem Int Ed 51:5911–5914

    Article  CAS  Google Scholar 

  28. Roters S, Appelt C, Westenberg H, Hepp A, Slootweg JC, Lammertsma K, Uhl W (2012) Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation. Dalton Trans 41:9033–9045

    Article  CAS  Google Scholar 

  29. Westenberg H, Slootweg JC, Hepp A, Kösters J, Roters S, Ehlers AW, Lammertsma K, Uhl W (2010) C≡C triple bond activation by heterocyclic aluminum phosphinides. Organometallics 29:1323–1330

    Article  CAS  Google Scholar 

  30. Karsch HH, Appelt A, Köhler F, Müller G (1985) (Phosphinomethyl)aluminum compounds: phosphinomethyl-bridged dimers and X-ray structures of [Me2AlCH2PMe2]2 and [ClAl(CH2PMe2)2]2. Organometallics 4:231–238

    Article  CAS  Google Scholar 

  31. Boudreau J, Courtemanche MA, Fontaine FG (2011) Reactivity of Lewis pairs (R2PCH2AlMe2)2 with carbon dioxide. Chem Commun 11131–11133

    Google Scholar 

  32. Dureen MA, Stephan DW (2009) Terminal alkyne activation by frustrated and classical Lewis acid/phosphine pairs. J Am Chem Soc 131:8396–8397

    Article  CAS  Google Scholar 

  33. Ménard G, Stephan DW (2012) C–H activation of isobutylene using frustrated Lewis pairs: aluminium and boron σ-allyl complexes. Angew Chem Int Ed 51:4409–4412

    Article  Google Scholar 

  34. Menard G, Stephan DW (2010) Room temperature reduction of CO2 to methanol by Al-based frustrated Lewis pairs and ammonia borane. J Am Chem Soc 132:1796–1797

    Article  CAS  Google Scholar 

  35. Menard G, Stephan DW (2011) Stoichiometric reduction of CO2 to CO by aluminium-based frustrated Lewis pairs. Angew Chem Int Ed 50:8396–8399

    Article  CAS  Google Scholar 

  36. Zhang Y, Miyake GM, Chen EYX (2010) Alane-based classical and frustrated Lewis pairs in polymer synthesis: rapid polymerisation of MMA and naturally renewable methylene butyrolactones into high-molecular-weight polymers. Angew Chem Int Ed 49:10158–10162

    Article  CAS  Google Scholar 

  37. Himbert G, Naßhahn H, Gerulat O (1997) A straightforward synthesis of silylated and stannylated ynamines and ynehydrazines. Synthesis 293–294

    Google Scholar 

  38. Holtrichter–Rößmann T, Rösener C, Hellmann J, Uhl W, Würthwein EU, Fröhlich R, Wibbeling B (2012) Generation of weakly bound Al–N Lewis pairs by hydroalumination of ynamines and the activation of small molecules: phenylethyne and dicyclohexylcarbodiimide. Organometallics 31:3272–3283

    Article  Google Scholar 

  39. Zheng W, Pi C, Wu H (2012) An alkynylaminomethylaluminium species with a six-membered chair conformation Al2C2N2 framework: a new path to geminal N/Al frustrated Lewis pairs. Organometallics 31:4072–4075

    Article  CAS  Google Scholar 

  40. Chakraborty D, Chen EXY (2002) Neutral olefin polymerisation activators as highly active catalysts for ROP of heterocyclic monomers and for polymerization of styrene. Macromolecules 35:13–15

    Article  CAS  Google Scholar 

  41. Baidossi W, Rosenfeld A, Wassermann BC, Schutte S, Schumann H, Blum J (1996) [(3-Dimethylamino)propyl]dimethylaluminum: a convenient reagent for methylation and ethynylation of carbonyl compounds. Synthesis 1127

    Google Scholar 

  42. Yasuda A, Tanaka S, Oshima K, Yamamoto H, Nozaki H (1974) Organoaluminum reagents of type R1R2NAlEt2 which allow regiospecific isomerization of epoxides to allylic alcohols. J Am Chem Soc 97:3252

    Google Scholar 

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Author information

Authors and Affiliations

  1. Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität, Corrensstrasse 30, 48149, Münster, Germany

    Werner Uhl

  2. Organisch-chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, 48149, Münster, Germany

    Ernst-Ulrich Würthwein

Authors
  1. Werner Uhl
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  2. Ernst-Ulrich Würthwein
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Correspondence to Werner Uhl .

Editor information

Editors and Affiliations

  1. Organisch-Chemisches Institut, Universität Münster, Corrensstr. 40, Münster, 48149, Germany

    Gerhard Erker

  2. , Department of Chemistry, University of Toronto, St. George Street 80, Toronto, M5S 3H6, Ontario, Canada

    Douglas W. Stephan

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Uhl, W., Würthwein, EU. (2012). Novel Al-Based FLP Systems. 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_374

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