UNIVERSITY OF JYVSKYL

-Hydride Elimination

Mikko Leskinen
Pihko Research Group
Literature Seminar
31.1.2012
UNIVERSITY OF JYVSKYL

General Trends for -Hydride

Elimination

McMillen, D. F.; Golden, D. M. Ann. Rev. Phys. Chem. 1982, 33, 493.
Blanksby, S. J.; Ellison, G. B. Acc. Chem. Res. 2003, 36, 255.
Martinho Simes, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629
Ziegler, T. Pure & Appl. Chem. 1991, 63, 873. (DFT)
UNIVERSITY OF JYVSKYL

General Trends for -Hydride

Elimination

-donation >> -backbonding

b-Hydride elimination can occur when:

-Complex

there exists a site of coordinative unsaturation on the metal cis to the alkyl group
which corresponds to a site of electronic unsaturation (empty metal orbital).
the M-C-C-H unit can take up a coplanar conformation which brings the -hydrogen
in close enough proximity to the metal to form an agostic interaction.
the metal is electrophilic resulting in an agostic interaction that is primarily electron
donative in nature (i.e. -donation>>-backbonding).
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General Trends for -Hydride

Elimination

-Complex

-Hydride elimination is much more rapid for d2 and higher metals than for d0.
In general, the higher the electronegativity of metal, the higher rate of -hydride
elimination.
That is because agostic interaction with a -C-H bond is stronger for more electronegative
metals, as the main impact into this agostic interaction is -donation of C-H bond.
Morokuma, K. et al., J. Am. Chem. Soc. 1985, 107, 7109.
Crabtree, R. H. The Organometallic Chemistry of the Transition Metals 4th Ed. 2005, Wiley
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Agostic Interaction

Prout, K. et al., J. Chem. Soc. Chem. Commun. 1982, 802.

Original definition: to refer specifically to situations in which a hydrogen atom is

covalentlybonded to both a carbon and to a transition metal atom.
Brookhart, M.; Green, M. L. H. J. Organometall. Chem. 1983, 250, 395.

Redefined definition : distortion of an organometallic moiety which brings an

appended C-H bond into close proximity with the metal center.
Scherer, W.; McGrady, G. S. Angew. Chem., Int. Ed. Engl. 2004, 43, 1782.
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Agostic Interaction
Conclusive Evidence: Neutron
diffraction Studies

..showing the distorted octahedral coordination around the Fe atom with the
aliphatic H atom [H(IA)] occupying a coordination site. The C1-H1 distance of
1.164 (3) is the longest such separation ever observed in a crystalline
complex.
Harlow, R. L. et al., J. Am. Chem. Soc. 1980, 102, 981.
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Agostic Interaction: Computational

Studies

Morokuma, K. et al., J. Am. Chem. Soc. 1985, 107, 7109.

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Agostic Interaction: Computational

Studies

Computational studies suggest that the higher energy of the Ni(II) vacant d orbital (0.1069 hartree)
with respect to that of the analogous Pd(II) complex (0.0505 hartree) results in a weaker donative
agostic interaction with the CH bond. The energetically optimized geometries of the agostic
complexes show a greater lengthening of the C-H bond in the Pd(II) complex than in the Ni(II)
complex, indicative of greater -donation in the former. These computational results are consistent
the experimentally observed greater stability of Ni alkyls towards -hydride elimination that Pd alkyls
and can be rationalized based on the greater electronegativity of Pd(II) vs Ni(II) as reflected in their
respective second ionization potentials.

Morokuma, K. et al., J. Am. Chem. Soc. 1985, 107, 7109.

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Kinetics

Only if the elimination itself is rate limiting we will see a kinetic isotopic effect for
elimination of H over D.
When hydrogens and deuteriums can be competitively abstracted, isotope effects
ranging from 2 to 4 are seen.
Ligand loss is often rate determing for -hydride elimination (but not always).
There must also be an empty orbital ready to accept the pair of electrons that
constitutes the -C-H bond.
A. Yamamoto et al., J. Organomet. Chem. 1976, 120, 257.
B. D. L. Reger and E. C. Culbertson, J. Am. Chem. Soc. 1976, 98, 2789.
Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry
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Stereochemistry of -Hydride
Elimination

Metalladibutyl and cycloheptane: The MCCH unit can take up a roughly

coplanar conformation which brings the -hydrogen close to the metal
Metallacyclopentane: The -hydrogen cannot achieve a synperiplanar
arrangement with the metal, and the elimination is greatly retared

G. M. Whitesides et al., J. Am. Chem. Soc. 1972, 94, 5258.

Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry
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Control of -Hydride Elimination: No -

Hydride

The alkyl is oriented so that the beta position cannot access the metal center
(steric bulk or rigidity).
The alkyl would give an unstable alkene as the product.
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Control of -Hydride Elimination:

Occupying the free coordination site.

-hydrogen elimination is inhibited by rendering the intermediate metal complex

four-coordinate, which prevents the generation of open coordination sites
necessary for -hydrogen elimination.

Whitesides, G. M.; Gaasch, J. F.; Stedronsky, E. R. J. Am. Chem. Soc. 1972, 94, 5258.
UNIVERSITY OF JYVSKYL

Control of -Hydride Elimination:

Occupying the free coordination site.

Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc. 1997 119, 12382.

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Control of -Hydride Elimination:

Occupying the free coordination site.

Excess of Br-ligand inhibits the reaction by quenching the open site.

Z. Wang and X. Lu, J. Org. Chem. 1996, 61, 2254.

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Smart Ways to Take Advantage of -

Hydride Elimination: The Asymmetric
Heck Reaction

Loiseleur, O.; Meier, P.; Pfaltz, A. Angew. Chem. Int. Ed. Engl. 1996, 35, 200.
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Smart Ways to Take Advantage of -

Hydride Elimination: The Asymmetric
Heck Reaction

Heres the innovative logic: If we use a cyclic olefin, we isomerize the bond. This
Means we arent making a C-C bond between to sp2-hybridized bonds, we are
making a sp2-sp3 bond. And sp3 center can be chiral.

Loiseleur, O.; Meier, P.; Pfaltz, A. Angew. Chem. Int. Ed. Engl. 1996, 35, 200.
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Smart Ways to Take Advantage of -

Hydride Elimination: -Arylation

Renaudat, A.; Jean-Grard, L.; Jazzar, R.; Kefalidis, C. E.; Clot, E.; Baudoin, O. Angew. Chem. Int. Ed. 2010, 49, 7261.
Larini, P.; Kefalidis, C. E.; Jazzar, R.; Renaudat,A.; Clot, E.; Baudoin, O. Chem. Eur. J. 2012, ASAP.
UNIVERSITY OF JYVSKYL

Smart Ways to Take Advantage of -

Hydride Elimination: -Arylation

Renaudat, A.; Jean-Grard, L.; Jazzar, R.; Kefalidis, C. E.; Clot, E.; Baudoin, O. Angew. Chem. Int. Ed. 2010, 49, 7261.
Larini, P.; Kefalidis, C. E.; Jazzar, R.; Renaudat,A.; Clot, E.; Baudoin, O. Chem. Eur. J. 2012, ASAP.
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Smart Ways to Take Advantage of -

Hydride Elimination: Dehydrogenative
Diels-Alder

The First dehydrogenative Diels-Alder

Stang, E. M.; White, C. M. J. Am. Chem. Soc. 2011, 133, 14892.

UNIVERSITY OF JYVSKYL

Smart Ways to Take Advantage of -

Hydride Elimination: Dehydrogenative
Diels-Alder

Stang, E. M.; White, C. M. J. Am. Chem. Soc. 2011, 133, 14892.

UNIVERSITY OF JYVSKYL

Smart Ways to Take Advantage of -

Hydride Elimination: Dehydrogenative
Diels-Alder

Stang, E. M.; White, C. M. J. Am. Chem. Soc. 2011, 133, 14892.

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Conclusions

The use of a coordinating ligand (co-catalyst) may

prevent the formation of vacant coordination sites
nessecary for -hydride elimination.
Control of -hydride elimination will make the transition
metal-catalyzed reactions more diversified.