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Low Valent, Low Coordinate Complexes Using Bulky Ligands 01/14/2015 Presented By Michael C. Young Topics Two and three coordinate low valent complexes of Ni Work by the Hillhouse Group Bulky m-terphenyl isonitrile ligands for low

  1. Low Valent, Low Coordinate Complexes Using Bulky Ligands 01/14/2015 Presented By Michael C. Young

  2. Topics • Two and three coordinate low valent complexes of Ni ● Work by the Hillhouse Group • Bulky m-terphenyl isonitrile ligands for low coordinate transition metal complexes ● Work by the Figueroa Group • Low coordinate complexes of Fe and Co ● Work by the Betley Group

  3. Monomeric Terminal Ni(II)-Imido • Impetus: At the time there was a dearth of examples of nickel complexes with hard imido ligands. • To prevent dimerization, it was desirable to use both a bulky phosphine ligand as well as a bulky nitrogen. 3 5 Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc. , 2001 , 123 , 4623.

  4. Monomeric Ni(II)-Phosphinidene • Similarly, there was no good example of a phosphinidene complex, and the imido synthesis suggested the analogous phosphinidene should be easily obtained. 5 6 Melenkivitz, R.; Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc. , 2002 , 124 , 3846.

  5. Ni(II)-Carbene and Reactions • Although Ni(II)-diazo complexes were known, it should be possible to extrude nitrogen to give a carbene. 4 5 7 Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc. , 2002 , 124 , 9976.

  6. Ni(II)-Imido Transfer Reactions • The formed imidos can be used for nitrene transfer reactions. Mindiola, D. J.; Hillhouse, G. L. Chem. Commun. , 2002 , 1840.

  7. Ni(II)=X Group Transfer with C2H4 • All of the Ni(II)=X species thus far discussed can react with olefins Waterman, R.; Hillhouse, G. L. J. Am. Chem. Soc. , 2003 , 125 , 13350.

  8. Ni(II)=P Transfer with Alkynes Waterman, R.; Hillhouse, G. L. Organometallics , 2003 , 22 , 5182.

  9. Unsaturated Ni(I) vs Ni(II)-C Species • Organolithiums can also be added to Ni(I) to give monoalkyls Kitiachvili, K. D.; Mindiola, D. J.; Hillhouse, G. L. Organometallics , 2004 , 126 , 10554.

  10. Ni(0) Coordination of N2 and NO • N2 binds in a side-on fashion at low temperature Iluc, V. M.; Miller, A. J. M.; Hillhouse, G. L. Organometallics , 2005 , 127 , 5091.

  11. Ni(0) Coordination of N3 • Unsurprisingly, azides can also form stable adducts with this complex. Waterman, R.; Hillhouse, G. L. J. Am. Chem. Soc. , 2008 , 130, 23628.

  12. Dicoordinate Ni(I) and Reactions Laskowski, C. A.; Hillhouse, G. L. J. Am. Chem. Soc. , 2008 , 130 , 13846.

  13. Insertion into Ni(II)-Alkyl Bonds Curley, J. J.; Kitiachvili, K. D.; Waterman, R.; Hillhouse, G. L. Organometallics , 2009 , 28 , 2568.

  14. Ni-CarbeneTransfer Harrold, N. D.; Waterman, R.; Hillhouse, G. L.; Cundari, T. R. J. Am. Chem. Soc. , 2009 , 131 , 12872.

  15. Catalytic Route to Diimides Laskowski, C. A.; Hillhouse, G. L. Organometallics , 2009 , 28 , 6114.

  16. Catalytic Route to Diimides Laskowski, C. A.; Hillhouse, G. L. Organometallics , 2009 , 28 , 6114.

  17. Towards a Ni(II)-Silylene Complex Iluc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc., 2010 , 132 , 11890.

  18. Reactions of Ni(0) and Ni(I) with CX 2 Anderson, J. S.; Iluc, V. M.; Hillhouse, G. L. Inorg. Chem. , 2010 , 49 10203.

  19. Ni(I)-XHR to Ni(II)=X Radical Pathway Iluc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc., 2010 , 132 , 15148.

  20. Dicoordinate Ni(II) Complexes Laskowski, C. A.; Miller, A. J. M.; Hillhouse, G. L.; Cundari, T. R. J. Am. Chem. Soc. , 2011 , 133 , 771.

  21. Ni(II)-Carbene-Bridged Dimers Laskowski, C. A.; Hillhouse, G. L. Chem. Sci. , 2010 , 2 , 321.

  22. Ni(III)-Imido Complex A terminal Ni(III)-imido should be exceptionally reactive and therefore unstable. • Iluc, V. M.; Miller, A. J. M.; Anderson, J. S.; Monreal, M. J.; Mehn, M. P.; Hillhouse, G. L. J. Am. Chem. Soc ., 2011 , 133 , 13055.

  23. Bis-NHC-Ni Complexes Harrold, N. D.; Hillhouse, G. L. Chem. Sci. , 2013 , 4 , 4011.

  24. Bis-NHC-Ni Complexes Harrold, N. D.; Hillhouse, G. L. Chem. Sci. , 2013 , 4 , 4011.

  25. Towards NHC-Ni(I) Alkyl Complexes Laskowski, C. A.; Bungum, D. J.; Baldwin, S. M.; Del Ciello, S. A.; Illuc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc., 2013 , 135 , 18272.

  26. 3-Coordinate Ni(II) Carbenes Iluc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc. , 2014 , 136 , 6479.

  27. Isocyano Ligands and Cu(I) Fox, B. J.; Sun, Q. Y.; DiPasquale, A. G.; Fox, A. R.; Rheingold, A. L.; Figueroa, J. S. Inorg. Chem. , 2009 , 131 , 11318.

  28. Isocyano Ligands with Ni(0) Fox, B. J.; Millard, M. D.; DiPasquale, A. G.; Rheingold, A. L.; Figueroa, J. S. Angew. Chem., Int. Ed., 2009 , 48, 3473. Emerich, B. M.; Moore, C. E.; Fox, B. J.; Rheingold, A. L.; Figueroa, J. S. Organometallics , 2011 , 30 , 2598.

  29. 2-Coordinate Pd(0) with Isocyano Ligands Labios, L. A.; Millard, M. D.; Rheingold, A. L.; Figueroa, J. S. J. Am. Chem. Soc. , 2009 , 131 , 11318.

  30. Ligand C−H Amination with Fe(II) Replacing Fe(II) with Zn(II) shuts down the reaction. • King, E. R.; Betley, T. A. Inorg. Chem. , 2009 , 48 , 2361.

  31. Complexes of Dipyrromethane King, E. R.; Betley, T. A. J. Am. Chem. Soc. , 2009 , 131 , 14379.

  32. Complexes of Dipyrromethane King, E. R.; Hennessy, E. T.; Betley, T. A. J. Am. Chem. Soc. , 2011 , 133 , 4917.

  33. Complexes of Dipyrromethane The reaction of 1 with adamantyl amine in toluene gives 6.7 turnover (amine 95%, imine 2.8%, • adamantylamine 1.8%). Product inhibited by anything that outcompetes azide for chelation. • KIE is consistent with H abstraction being the RDS. • King, E. R.; Hennessy, E. T.; Betley, T. A. J. Am. Chem. Soc. , 2011 , 133 , 4917.

  34. Complexes of Dipyrromethane King, E. R.; Hennessy, E. T.; Betley, T. A. J. Am. Chem. Soc. , 2011 , 133 , 4917.

  35. Electronic Perturbation of Ligands Scharf, A. B.; Betley, T. A. Inorg. Chem. , 2011 , 50 , 6837.

  36. Co(III) Complexes of Dipyrromethane King, E. R.; Sazama, G. T.; Betley, T. A. J. Am. Chem. Soc. , 2012 , 134 , 17858.

  37. Intramolecular Cyclization of Alkyl Azides Based on the previous results, the group next wanted to explore the substrate scope of their • nitrene insertion into aliphatic C−H bonds. Hennessy, E. T.; Betley, T. A. Science , 2013 , 340 , 591.

  38. Intramolecular Cyclization of Alkyl Azides Hennessy, E. T.; Betley, T. A. Science , 2013 , 340 , 591.

  39. Intramolecular Cyclization of Alkyl Azides Hennessy, E. T.; Betley, T. A. Science , 2013 , 340 , 591.

  40. Intramolecular Cyclization of Alkyl Azides As the substrates become more complex, so too are the product(s). • Hennessy, E. T.; Betley, T. A. Science , 2013 , 340 , 591.

  41. Intramolecular Cyclization of Alkyl Azides Hennessy, E. T.; Betley, T. A. Science , 2013 , 340 , 591.

  42. Thank you for your attention! http://www.phdcomics.com/comics.php?f=1768, Accessed 01/14/2015.

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