Ligands 01/14/2015 Presented By Michael C. Young Topics Two and - - PowerPoint PPT Presentation

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Ligands 01/14/2015 Presented By Michael C. Young Topics Two and - - PowerPoint PPT Presentation

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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

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Low Valent, Low Coordinate Complexes Using Bulky Ligands

01/14/2015 Presented By Michael C. Young

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SLIDE 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
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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.

Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc., 2001, 123, 4623.

3 5

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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.

Melenkivitz, R.; Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc., 2002, 124, 3846.

5 6

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SLIDE 5

Ni(II)-Carbene and Reactions

  • Although Ni(II)-diazo complexes were known, it should be possible to extrude nitrogen to give a

carbene.

Mindiola, D. J.; Hillhouse, G. L. J. Am. Chem. Soc., 2002, 124, 9976.

5 4 7

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SLIDE 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.

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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.

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SLIDE 8

Ni(II)=P Transfer with Alkynes

Waterman, R.; Hillhouse, G. L. Organometallics, 2003, 22, 5182.

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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.

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SLIDE 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.

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SLIDE 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.

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SLIDE 12

Dicoordinate Ni(I) and Reactions

Laskowski, C. A.; Hillhouse, G. L. J. Am. Chem. Soc., 2008, 130, 13846.

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SLIDE 13

Insertion into Ni(II)-Alkyl Bonds

Curley, J. J.; Kitiachvili, K. D.; Waterman, R.; Hillhouse, G. L. Organometallics, 2009, 28, 2568.

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SLIDE 14

Ni-CarbeneTransfer

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

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Catalytic Route to Diimides

Laskowski, C. A.; Hillhouse, G. L. Organometallics, 2009, 28, 6114.

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Catalytic Route to Diimides

Laskowski, C. A.; Hillhouse, G. L. Organometallics, 2009, 28, 6114.

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SLIDE 17

Towards a Ni(II)-Silylene Complex

Iluc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc., 2010, 132, 11890.

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Reactions of Ni(0) and Ni(I) with CX2

Anderson, J. S.; Iluc, V. M.; Hillhouse, G. L. Inorg. Chem., 2010, 49 10203.

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SLIDE 19

Ni(I)-XHR to Ni(II)=X Radical Pathway

Iluc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc., 2010, 132, 15148.

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SLIDE 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.

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Ni(II)-Carbene-Bridged Dimers

Laskowski, C. A.; Hillhouse, G. L. Chem. Sci., 2010, 2, 321.

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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.

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SLIDE 23

Bis-NHC-Ni Complexes

Harrold, N. D.; Hillhouse, G. L. Chem. Sci., 2013, 4, 4011.

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SLIDE 24

Bis-NHC-Ni Complexes

Harrold, N. D.; Hillhouse, G. L. Chem. Sci., 2013, 4, 4011.

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SLIDE 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.

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SLIDE 26

3-Coordinate Ni(II) Carbenes

Iluc, V. M.; Hillhouse, G. L. J. Am. Chem. Soc., 2014, 136, 6479.

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SLIDE 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.

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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.

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SLIDE 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.

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SLIDE 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.

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SLIDE 31

Complexes of Dipyrromethane

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

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SLIDE 32

Complexes of Dipyrromethane

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

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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.

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SLIDE 34

Complexes of Dipyrromethane

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

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SLIDE 35

Electronic Perturbation of Ligands

Scharf, A. B.; Betley, T. A. Inorg. Chem., 2011, 50, 6837.

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SLIDE 36

Co(III) Complexes of Dipyrromethane

King, E. R.; Sazama, G. T.; Betley, T. A. J. Am. Chem. Soc., 2012, 134, 17858.

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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.

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Intramolecular Cyclization of Alkyl Azides

Hennessy, E. T.; Betley, T. A. Science, 2013, 340, 591.

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SLIDE 39

Intramolecular Cyclization of Alkyl Azides

Hennessy, E. T.; Betley, T. A. Science, 2013, 340, 591.

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SLIDE 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.

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SLIDE 41

Intramolecular Cyclization of Alkyl Azides

Hennessy, E. T.; Betley, T. A. Science, 2013, 340, 591.

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Thank you for your attention!

http://www.phdcomics.com/comics.php?f=1768, Accessed 01/14/2015.