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Cooperative ( Dinucleating ) systems for E-H Bond activation

Linda S. Jongbloed , S. Y. de Boer, J. N. H. Reek, J. I. van der Vlugt . Cooperative ( Dinucleating ) systems for E-H Bond activation. Homogeneous and Supramolecular Catalysis van ‘t Hoff Institute for Molecular Sciences University of Amsterdam. EWPC 19 March 2013.

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Cooperative ( Dinucleating ) systems for E-H Bond activation

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  1. Linda S. Jongbloed, S. Y. de Boer, J. N. H. Reek, J. I. van der Vlugt Cooperative (Dinucleating) systems for E-H Bond activation HomogeneousandSupramolecularCatalysis van ‘t Hoff Institute for Molecular Sciences University of Amsterdam EWPC 19 March 2013

  2. E-H activationandcatalysis Hydroamination: Activation of N-H, O-H, S-H andsubsequentcatalyticreactionssuch as hydroadditionreactions

  3. Cooperative ligand systems • Spectator ligands • Oxidation state of metal raiseswith 2 • Non-innocent ligands • No formal change in oxidation state of metal • Ligand participates in catalyticcycle J. I. van der Vlugt, Eur. J. Inorg. Chem.2012, 3, 363-375

  4. Cooperative ligands: examples Noyori Hydrogenation of ketones Ikariya Intramolecularhydroamination Grützmacher Hydrogenation T. Ikariya, K. Murata, R. Noyori, Org. Biomol. Chem. 2006, 4, 393. Y. Kashiwame, S. Kuwata, T. Ikariya, Chem. Eur. J.2010, 16, 766. P. Maire, T. Büttner, F. Breher, P. Le Floch, H. Grützmacher, Angew. Chem. Int. Ed. 2005, 117, 6477

  5. Cooperative ligands: examples Milstein Hydrogenation, hydrogenolysis, dehydrogenativecoupling van der Vlugt S-H activation, C-C coupling C. Gununanathan, D. Milstein, Acc. Chem. Res201, 44, 588-602. J. I. van der Vlugt, E. A. Pidko, R. C. Bauer, Y. Gloaguen, M. K. Rong, M. Lutz, Chem. Eur. J. 2011, 17, 3850. J. I. van der Vlugt, E. A. Pidko, D. Vogt, M. Lutz, A. L. Spek, Inorg. Chem. 2009, 48, 7513-7515. J. I. van der Vlugt, J. N. H. Reek, Angew. Chem. Int. Ed. 2009, 48, 8832-8846.

  6. Dinuclearactivation In enzymes, active sites often have dinuclearcores Combine bimetalliccooperativitywith ligand non-innocence F. Gloaguen and T. B. Rauchfuss, Chem. Soc. Rev., 2009, 38, 100–108.

  7. Goals • Development of new cooperative ligands with proton transfer reactivity • Dinucleating ligands • Activation of E-H bonds andsubsequenthydroadditionreactions

  8. Design new ligands • PN: Bidentatevstridentate- additional vacant site • PN(C): uniquetype of cooperativity PNP: occupationof threecoordination sites Activation of substratespossible Subsequenthydroadditionsnotyetaccomplished

  9. PN ligand- Pd X • Isolation leads to decomposition JP-P = 439 Hz S. Y. de Boer, Y. Gloaguen, J. N. H. Reek, M. Lutz, J. I. van der Vlugt, Dalton Trans. 2012, 41, 11276-11283

  10. CNP ligand Reversibleorthometalation? Dearomatizationreactivity Unexpectedorthometalation is observed Phosphorus is strong trans ligand – reversibleorthometalation? Versatile ligand withtwocooperative sites

  11. CNP ligand - Pd: N-H activation • Reversibleorthometalation Dearomatization

  12. CNP ligand - Pd: N-H activation 31P NMR spectra A B C D

  13. CNP ligand - Rh: reactivity ? = agostic C-H, π-interaction of phenyl ring, CH2Cl2 Rh-C canbecleavedby strong electrophiles Alsobyweakacids (NH4PF6, HCOOH) So far no N-H activation

  14. CNP ligand - Rh 31P NMR spectra A JRh-P 101 Hz JRh-P 163 Hz B JRh-P 170 Hz C JRh-P 203 Hz D

  15. Dinucleating ligand Bimetallic rhodium complex shows similarbehaviour as mono-nuclear complex Palladium complex does not show desiredreactivity Investigations in bimetallicactivations are ongoing

  16. Conclusions • PN ligand • CNP ligand • Dearomatization • Reversible C-H activation

  17. Acknowledgements Sandra Y. de Boer MSc. Dr. Ir. Jarl Ivar van der Vlugt Prof. dr. Bas de Bruin Prof. dr. Joost N. H. Reek

  18. CNP ligand - Rh: S-H activation Unexpected de-coordination of pyridine moiety Alsopossiblewitharomaticandbenzylicmercaptans

  19. Hydroamination • Challenges in hydroamination: • Intermolecularhydroamination • Linearanti-Markovnikov product • Hydroaminationwithprimaryaminesand ammonia (NH3)

  20. Aim • Gainfundamentalunderstandingandinsight in activationprocessesandsubsequentreactivity • Improvesyntheticmethodologiesfororganic / pharmaceuticalprocesses • Atom efficiency • Neutral conditions

  21. Research start Ligand design: pyridine dearomatization

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