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Published online on April 18, 2007, 10.1073/pnas.0610747104
PNAS | April 24, 2007 | vol. 104 | no. 17 | 6908-6914


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Coordination Chemistry of Saturated Molecules Special Feature
COORDINATION CHEMISTRY OF SATURATED MOLECULES SPECIAL FEATURE / REVIEW
Agostic interactions in transition metal compounds

Maurice Brookharta,b, Malcolm L. H. Greenb,c, and Gerard Parkinb,d

aDepartment of Chemistry, University of North Carolina, Chapel Hill, NC 27599-3290, cInorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX13QR, United Kingdom; and dDepartment of Chemistry, Columbia University, New York, NY 10027

Edited by John E. Bercaw, California Institute of Technology, Pasadena, CA, and approved February 23, 2007 (received for review February 8, 2007)

The impact of agostic interactions (i.e., 3-center–2-electron MFormula HFormula C bonds) on the structures and reactivity of organotransition metal compounds is reviewed.


Author contributions: M.B., M.L.H.G., and G.P. wrote the paper.

The authors declare no conflict of interest.

This article is a PNAS Direct Submission.

e For a review of {alpha}- and beta-hydrogen elimination processes, see ref. 1.

f Although there are two reports of complexes in which alkanes are in the vicinity of the metal center (refs. 20 and 21), there is no spectroscopic evidence that the alkane remains coordinated to the metal in solution. Furthermore, for one of these complexes (ref. 21), both the metal and alkane are disordered so that the precise details of the interaction are uncertain.

g For recent examples of {sigma}-complexes that have been characterized by NMR spectroscopy, see refs. 22–24.

h For recent reviews, see refs. 25–27.

i For a recent example, see ref. 28.

j For other examples, see refs. 33–36.

k Venanzi and coworkers (37) also offered another interpretation for "pregostic": agostic of the weak type described by Pregosin.

l MFormula H–C interactions that are not agostic have also been referred to as pseudo-agostic (see ref. 39).

m For a recent analysis of MFormula H–C interactions in d8 Ni, Pd, and Pt compounds, see ref. 43.

n For a recent review of theoretical aspects of agostic interactions, see ref. 47.

o This view of the bonding in agostic compounds is necessarily simplistic. For a more detailed discussion, see ref. 48.

bTo whom correspondence may be addressed. E-mail: brookhar{at}email.unc.edu, malcolm.green{at}chemistry.ox.ac.uk, or parkin{at}columbia.edu

© 2007 by The National Academy of Sciences of the USA


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