Abstract
The past several decades have witnessed enormous growth in what we know about the synthesis, reactivity, reaction mechanisms, molecular structures, and electronic structures of organometallic molecules. Curiously, however, we know far less about the thermodynamics of most organometallic transformations and, in particular, about the exact strengths of metal-ligand bonds. In principle, such information offers a better understanding of metal-ligand bonding, a better insight into the course(s) of known reactions, and a valuable advantage in designing new transformations.1–5 For organometallic chemistry involving actinides, lanthanides, and early transition elements, our thermochemical/calorimetric investigations were motivated by growing evidence that deviations in reactivity patterns from those of middle and late transition elements could not be explained by kinetic factors alone. In the present chapter, we briefly review some of our recent results in this area, focusing upon how ancillary ligands affect metal-ligand bond enthalpies, metal-ligand bonding patterns as a function of position in the Periodic Table, and the thermochemically-assisted design of a new catalytic reaction pattern: organolanthanide-catalyzed hydroamination.
Keywords
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
T. J. Marks, ed., “ Metal-Ligand Bonding Energetics in Organotransition Metal Compounds”, Polyhedron Symposium-in-Print, (1988). 7.
G. Pilcher and H. A. Skinner, in “The Chemistry of the Metal-Carbon Bond,” F. R. Harley and S. Patai, eds., Wiley, New York, (1982) 43–90.
J. A. Connor, Top. Curr. Chem. 71: 110 (1977).
J. Halpern, Acc. Chem. Res. 15: 238 (1982).
J. U. Mondal and D. M. Blake, Coord. Chem. Rev. 47: 204 (1983).
J. W. Bruno, T. J. Marks, and L. R. Morss, J. Am. Chem. Soc. 105: 6824 (1983).
L. E. Schock and T. J. Marks, manuscript in preparation.
D. C. Sonnenberger, L. R. Morss, and T. J. Marks, Organometallics 4: 352 (1985)
J. W. Bruno, H. A. Stecher, L. R. Morss, D. C. Sonnenberger, and T. J. Marks, J. Am. Chem. Soc. 108: 7275 (1986)
L. E. Schock and T. J. Marks, J. Am. Chem. Soc. 110: 7701 (1988)
L. E. Schock, A. M. Seyam, M. Sabat, and T. J. Marks, in ref. 1, pp 1517–1530
S. P. Nolan, D. Stern, and T. J. Marks, J. Am. Chem. Soc. in press.
S. P. Nolan, D. Stern, and T. J. Marks, Abstracts, 196th ACS National Meeting, Los Angeles, CA, Sept. 25–30, 1988, INOR 378.
J. E. Huheey, “Inorganic Chemistry”, 2nd ed., Harper and Row, New York (1978), pp. 824–850.
D. D. Wagman, W. H. Evans, V. B. Parker, L. Halow, S. M. Bailey, R. H. Schumm, and K. L. Churney, Natl. Bur. Stand. Tech. Note (U.S.) 1971, No. 34–35.
Calculated from thermodynamic data given by: L. R. Morss, in “The Chemistry of the Actinide Elements”, 2nd ed., J. J. Katz, G. T. Seaborg, L. R. Morss, eds., Chapman and Hall, London (1986), Chapt.
A. R. Dias, M. S. Salema, and J. A. Martinho-Simoes, J. Organomet. Chem. 222: 69 (1981).
S. P. Nolan, R. Lopez de la Vega, S. L. Mukerjee, A. A. Gonzalez, K. Zhang, and C. D. Hoff, ref. 1, pp. 1491–1498.
J. A. Connor, M. T. Zarafani-Moattar, J. Bickerton, M. L. El Saied, S. Suradi, E. Caron, A. Al-Takhin, and H. A. Skinner, Organometallics 1:1166 (1982), and references therein.
J. U. Mondai and D. M. Blake, Coord. Chem. Rev. 47: 205 (1982).
P. 0. Stoutland, R. G. Bergman, S. P. Nolan, and C. D. Hoff, ref. 1, pp. 1429–1440.
R. L. Brainard and G. M. Whitesides, Organometallics 4: 1550 (1985).
J. B. Schilling, W. A. Goddard, III, and J. L. Beauchamp, J. Am. Chem. Soc. 109: 5573 (1987).
J. W. Bruno, M. R. Duttera, C. M. Fendrick, G. M. Smith, and T. J. Marks, Inorg. Chim. Acta 94: 271 (1984).
T. Ziegler, V. Tschinke, L. Versluis, and E. J. Baerends, in ref. 1, pp. 1625–1657.
L. Pauling, “The Nature of the Chemical Bond,” 3rd ed., Cornell University Press, Ithaca, New York, (1960), Chapter 3.
J. E. Huheey, “Inorganic Chemistry,” 3rd ed., Harper and Row, New York (1983) pp. 144–160.
B. E. Douglas, D. H. McDaniel, and J. J. Alexander, “Concepts and Models of Inorganic Chemistry,” 2nd ed., Wiley, New York (1983) Chapt. 24.
J. Mullay, Struct. Bond (Berlin) 66:1 (1987), and references therein.
R. L. Matcha, J. Am. Chem. Soc. 105:4859 (1983). We utilize the formulation having an arithmetic mean expression for D(A-B) since this leads more straightforwardly to useful relationships such as eq.(12). Both arithmetic and geometric mean approaches have been employed in the Pauling formulation, 26–28 with the latter preferred in cases of sign ambiguities.
Because D(I2)-D(Me2) is negative (a common artifact when the arithmetic mean is used in eq.(12)),28 we arbitrarily set it equal to zero in the expression analogous to eq.(13). This in no way affects the XM dependence of the function.
H. E. Bryndza, L. K. Fong, R. A. Paciello, W. Tam, and J. E. Bercaw, J. Am. Chem. Soc. 109: 1444 (1987).
H. Mauermann and T. J. Marks, Organometallics 4: 200 (1985).
G. Jeske, H. Lauke, H. Mauermann, P. N. Swepston, H. Schumann, and T. J. Marks, J. Am. Chem. Soc. 107: 8091 (1985).
G. Jeske, L. E. Schock, H. Mauermann, P. N. Swepston, H. Schumann, and T. J. Marks, J. Am. Chem. Soc. 107: 8103 (1985).
G. Jeske, H. Lauke, H. Mauermann, H. Schumann, and T. J. Marks, J. Am. Chem. Soc. 107: 8111 (1985).
CP2LaNMe2 catalyzes ethylene polymerization (D. Hedden and T. J. Marks, unpublished results).
P. J. Fagan, J. M. Manriquez, C. H. Vollmer, C. S. Day, V. Day, and T. J. Marks, J. Am. Chem. Soc. 103: 2206 (1981).
For the addition of NH3 to H2C=CH2, AG° —4 kcal/mol.
M. R. Gagné and T. J. Marks, J. Am. Chem. Soc. in press.
Y. Tamaru, M. Hojo, H. Higashima, and Z. Yoshida, J. Am. Chem. Soc. 110:3994 (1988), and references therein.
J. P. Collman, L. G. Hegedus, J. R. Norton, and R. G. Finke, “Principles and Applications of Organotransition Metal Chemistry,” University Science Books, Mill Valley, CA (1987), Chapts. 7.4, 17. 1.
A. L. Casalnuovo, J. C. Calabrese, and D. Milstein, J. Am. Chem. Soc. 110: 6738 (1988).
G. Pez, and J. E. Galle, Pure APD1. Chem. 57: 1917 (1985).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1990 Springer Science+Business Media New York
About this chapter
Cite this chapter
Gagne, M.R., Nolan, S.P., Seyam, A.M., Stern, D., Marks, T.J. (1990). Thermochemical Aspects of Organotransition Metal Chemistry. Insights Provided by Metal-Ligand Bond Enthalpies. In: Fackler, J.P. (eds) Metal-Metal Bonds and Clusters in Chemistry and Catalysis. Industry-University Cooperative Chemistry Program Symposia. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2492-6_9
Download citation
DOI: https://doi.org/10.1007/978-1-4899-2492-6_9
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4899-2494-0
Online ISBN: 978-1-4899-2492-6
eBook Packages: Springer Book Archive