Abstract
For many decades, biradicals have been assumed to be important intermediates in many thermally initiated and photochemical organic reactions. For the most part, they were postulated reaction intermediates because kinetic and stereochemical results were more readily explainable by assuming intermediates with properties presumed to be characteristic of biradicals. Until the 1970s, very few of these highly reactive species had been directly detected by physical techniques. In recent years, however, the situation has changed significantly, and now an increasing number of techniques are available to study their properties.(1) Recent progress in our laboratory has made it possible to add electron spin resonance to the list of tools with which to study highly reactive biradicals under normal reaction conditions.(2) This work is the topic of this chapter.
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References
W. T. Borden, ed., Diradicals, Wiley, New York (1982).
G. L. Closs, M. D. E. Forbes, and J. R. Norris, Jr., J. Phys. Chem. 91, 3592 (1987);
G. L. Closs and M. D. E. Forbes, J. Am. Chem. Soc. 109, 6185 (1987).
S. L. Buchwalter and G. L. Closs, J. Am. Chem. Soc. 97, 3857 (1975); 101, 4688 (1979);
R. Jain, G. J. Snyder, and D. A. Dougherty, J. Am. Chem. Soc. 106, 7294 (1984);
R. Jain, M. B. Sponsler, F. D. Corns, and D. A. Dougherty, J. Am. Chem. Soc. 110, 1356 (1988 ).
J. C. Scaiano, Acc. Chem. Res. 15, 252 (1982);
R. A. Caldwell, T. Majima, and C. Pac, J. Am. Chem. Soc. 104, 629 (1982);
J. C. Scaiano and P. J. Wagner, J. Am. Chem. Soc. 106, 4626 (1984);
L. J. Johnston, J. C. Scaiano, J.W. Sheppard, and J. P. Bays, Chem. Phys. Lett. 124, 493 (1986);
K. Akiyama, Y. Ikegami, and S. Tero-Kobuta, J. Am. Chem. Soc. 109, 2538 (1987);
R.A. Caldwell, H. Sakuragi, and T. Majima, J. Am. Chem. Soc. 106, 2471 (1984);
D. Weir and J. C. Scaiano, Chem. Phys. Lett. 118, 526 (1985);
M. B. Zimmt, C. Doubleday, Jr., LR. Gould, and N.J. Turro, J. Am. Chem. Soc. 107, 6724 (1985);
M. B. Zimmt, C. Doubleday, Jr., and N.J. Turro, J. Am. Chem. Soc. 107, 6726 (1985); 108, 3618 (1986);
L. J. Johnston and J. C. Scaiano, J. Am. Chem. Soc. 108, 2349 (1986).
H. D. Brauer, H. Stieger, J. S. Hyde, L. D. Kispert, and G. R. Luckhurst, Mol. Phys. 17, 457 (1969).
D. C. Reitz and S. I. Weissman, J. Chem. Phys. 33, 700 (1960).
G. R. Eaton and S. S. Eaton, Acc. Chem. Res. 21, 107 (1988).
Y. N. Molin, ed., Spin Polarization and Magnetic Effects in Radical Reactions, Elsevier, Amsterdam (1984);
L. T. Muus, P. W. Atkins, K. A. McLauchlan, and J. B. Pedersen,, eds., Chemically Induced Magnetic Polarization, Reidel, Dordrecht, Holland (1977).
K. A. McLauchlan and D. G. Stevens, Acc. Chem. Res. 21, 54 (1988).
A. D. Trifunac, M. C. Thurnauer, and J. R. Norris, J. Chem. Phys. 71, 4380 (1979).
A. D. Trifunac, M. C. Thurnauer, and J. R. Norris, Chem. Phys. Lett. 57, 471 (1978).
M. C. Thurnauer and D. Meisel, J. Am. Chem. Soc. 104, 3729 (1983).
G. L. Closs and C. Doubleday, Jr., J. Am. Chem. Soc. 95, 2735 (1973);
GL. Closs and O. D. Redwine, J. Am. Chem. Soc. 107, 4543, 6131 (1985).
J. K. Vollenweider, H. Fischer, J. Hennig, and R. Leuschner, Chem. Phys. 97, 217 (1985).
W. M. Horspool, Photochemistry, Vol. 19, London, Royal Chemical Society (1988), p. 151.
J. B. Pedersen, Theories of Chemically Induced Polarization, Odense University Press, Denmark (1979).
P. L. Corio, Structure of High-Resolution NMR Spectra, Academic Press, New York (1966), Chapter 5.
P. W. Atkins and G. T. Evans, Mol. Phys. 27, 1633 (1974).
H. Schuh, E. J. Hamilton, Jr., H. Paul, and H. Fischer, Helv. Chim. Acta 57, 2011 (1974).
N. Ohno, N. Kito, and Y. Ohnishi, Bull. Chem. Soc. Jpn. 44, 470 (1971).
G. L. Closs, R. J. Miller, and O. D. Redwine, Acc. Chem. Res. 18, 196 (1985).
J. A. Nairn and C. L. Braun, J. Chem. Phys. 74, 2441 (1981).
H. M. McConnell, J. Chem. Phys. 35, 508 (1961);
J. Halpern and L. E. Orgel, Disc. Faraday Soc. 29, 32 (1960).
K. Ohta, G. L. Closs, K. Morokuma, and N. J. Green, J. Am. Chem. Soc. 108, 1319 (1986); M. D. E. Forbes and G. L. Closs, unpublished results.
G. L. Closs, P. Piotrowiak, J. M. Maclnnis, and G. R. Fleming, J. Am. Chem. Soc. 110, 2652 (1988).
G. L. Closs and J. R. Miller, Science 240, 440 (1988).
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Closs, G.L., Forbes, M.D.E. (1990). EPR Study of Polymethylene Biradicals. In: Platz, M.S. (eds) Kinetics and Spectroscopy of Carbenes and Biradicals. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-3707-0_3
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