Abstract
For many years it was puzzling that metal atoms, which were not considered good Lewis acids, could form adducts with CO, considered to be a poor donor toward most Lewis acids. An example is the hexacarbonylchromium, Cr(CO)6. On the other hand, it was stressed that chromium, having 24 electrons, by accepting 6x2 electrons from 6 CO molecules, will fill its orbitals to a total of 36 electrons, which is the electron configuration of krypton. The LCAO approximation method (linear combination of atomic orbitals) helped to explain the stability of these adducts as being due to a two-way acid-base interaction between the metal and CO: the metal synergically interacts with CO, acting as an acid and a base, while CO simultaneously behaves as a donor and acceptor. In 1955 Ernst Otto Fischer, University of Munich, showed that an increase of the number of chromium electrons to 36 can be achieved by three π-electron pairs of benzene, like, e.g., in benzenetricarbonylchromium, (C6H6)Cr(CO)3. Cyclopentadienyl, C5H5 -, has also been known to form compounds with metal atoms.
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References
T. J. Kealy and P. L. Pauson, Nature, 1951, 168, 1039.
M. Rosenblum, Chemistry of the Iron Group Metallocenes, Interscience, New York 1965.
G. Wilkinson, J. Organomet. Chem. 1975, 100, 273.
J. S. Thayer, Adv. Organomet. Chem. 1975, 13, 1.
K. F. Purcell and J. C. Kotz, Inorganic Chemistry, W. B.Saunders, Philadelphia 1977, p. 877.
C. A. Tolman, Chem. Soc. Rev.Chem. Soc. Rev. 1972,1, 337.
F. A. Cotton, J. Organomet. Chem. 1975, 100, 29.
M. Green, D. M. Grove, J. A. K. Howard, J. L. Spencer, and F. G. A. Stone, J. Chem. Soc, Chem. Commun. 19761976, 759.
Ref. 4, pp. 1-49.
F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley, New York 1988, pp. 78–83.
J. Howard, J. Chem. Soc, Dalton Trans. 1982, 967.
R. K. Bohn and A. Haaland, J. Organomet. Chem. 1966, 5, 470.
G. J. Palenik, Inorg. Chem. 1970, 9, 2424.
R. L. Sime and R. J. Sime, J. Am. Chem. Soc. 1974, 96, 892.
M. Cais, Organomet. Chem. Rev. 1966, 1, 435.
T. G. Traylor and J. C. Ware, J. Am. Chem. Soc. 1967, 89, 2304.
T. D. Turbitt and W. E. Watts, J. Chem. Soc, Perkin Trans. 2, 1974, 177, and refs. therein.
J. W. Larsen and P. Ashkenazi, J. Am. Chem. Soc. 1975, 97, 2140.
C. C. Lee, S. C. Chen, W J. Pannekoek, and R. G. Sutherland, J. Organomet. Chem. 1976, 118, C47.
M. Hisatome and K. Yamakawa, J. Organomet. Chem. 1977, 133, C9.
W.E. Watts, J. Chem. Soc, Perkin Trans. 1976, 1, 804.
S. Ursic and S. Ašperger, J. Inorg. Nucl. Chem. 1979, 41, 1329, and refs. therein.
R. Gleiter and R. Seeger, Helv. Chim. Acta, 1971, 54, 1217.
M. J. Nugent, R. E. Carter, and J. H. Richards, J. Am. Chem. Soc 1969, 91, 6145.
M. Cais, J. J. Dannenberg, A. Eisenstadt, M. L. Levenberg, and J. H. Richards, Tetrahedron Lett. 1966, 1695.
M. Hisatome and K. Yamakawa, Tetrahedron Lett. 1971, 27, 2101; ibid, 3533.
J. J. Dannenberg, M. L. Levenberg, and J. H. Richards, Tetrahedron, 1973, 29, 1575.
A. Streitwieser, Jr., and R. C. Fahey, Chem. Ind. (London) 1957, 1417.
W. H. Saunders, Jr., S. Ašperger, and D. H. Edison, Chem. Ind. (London), 1957, 1417.
A. Streitwieser, Jr., R. H. Jagow, R. C. Fahey, and S. Suzuki, J. Am. Chem. Soc. 1958, 80, 2326.
W. H. Saunders, Jr., S. Ašperger, and D. H. Edison, J. Am. Chem. Soc 1958, 80, 2421.
K. Mislow, S. Borcic, and V. Prelog, Helv. Chim. Acta, 1957, 40, 2477.
R. R. Johnson and E. S. Lewis, Proc. Chem. Soc 1958, 52.
D. E. Sunko and S. Borcic, ACS Monogr. No. 167, Chap. 3; L. Melander and W H. Saunders, Jr., Reaction Rates of Isotopic Molecules, Wiley, New York 1980; A. Thibblin and P. Ahlberg, Chem. Soc. Rev. 1989, 18, 209-224.
D. E. Sunko, Croat. Chem. Acta, 1996, 69, 1275–1304.
K. C. Westway in: E. Buncel and C. C. Lee, Eds., Isotopes in Organic Chemistry, Vol. 7, Elsevier, Amsterdam 1987, Chap. 5.
B. Capon and S. P. Mc Manus. Neighboring Group Participation, Plenum Press, New York 1976.
D. T. Stoelting and V. J. Shiner, Jr., J. Am. Chem. Soc. 1993, 115, 1695; V. J. Shiner and F. P. Wilgis, in: E. Buncel and W. H. Saunders Jr., Eds., Isotopes in Organic Chemistry, Vol. 8, Elsevier, Amsterdam 1992, Chap. 6; V. J. Shiner, Jr., T. E. Neumann, and B. B. Basinger, Croat Chem. Acta, 1996, 69, 1405.
Y. Zhang, J. Bommuswamy, and M. L. Sinnott, J. Am. Chem. Soc. 1994, 116, 7557.
S. Ašperger, D. Pavlović, Z. Kukrić, and D. Šutić, Inorg. Chim. Acta, 1990, 171, 5.
V. J. Shiner, Jr., ACS Monogr. No. 167, 1970, p. 104.
A. Streitwieser, Jr. and G. A. Daffon, Tetrahedron Lett. 1969, 1263.
V. J. Shiner, Jr., M. W. Rapp, E. A. Halevi, and M. Wolfsberg, J. Am. Chem. Soc. 1968, 90, 7171.
M. Schwarz, Ed., Ions and Ion Pairs in Organic Reactions, Vol. 2, Wiley, New York 1974, pp. 297–329.
B. Goričnik, Z. Majerski, S. Borčić, and D. E. Sunko, J. Org. Chem. 1973, 38, 1881.
D. Šutić, S. Ašperger, and S. Borčić, Org. Chem. 1982, 47, 5120.
E. A. Hill and J. H. Richards, J. Am. Chem. Soc. 1961, 83, 3840.
S. Winstein and R. Heck, J. Am. Chem. Soc. 1956, 78, 4801.
S. Winstein and G. C. Robinson, J. Am. Chem. Soc. 1958, 80, 169.
S. Ašperger, Z. Kukrić, W. H. Saunders, Jr., and D. Šutić, J. Chem. Soc, Perkin. Trans. 2, 1992, 275.
S. R. Hartshorn and V. J. Shiner, Jr., J. Am. Chem. Soc. 1972, 94, 9002.
E. G. Perevalova, Yu. A. Ustynyuk, and A. N. Nesmeyanov, Izv. Akad. Nauk SSSR, Otd. Khim. Nauk, 1963, 1036.
W. H. Saunders, Jr., J. Am. Chem. Soc. 1985, 107, 164.
M. Amin, R. C. Price, and W. H. Saunders, Jr., J. Am. Chem. Soc. 1990, 112, 4467.
L. Melander and W. H. Saunders, Jr., Reaction Rates of Isotopic Molecules, Wiley-Interscience, New York 1980, pp. 140–152.
S. Winstein and G. C. Robinson, J. Am. Chem. Soc. 1958, 80, 169.
C. A. Bunton, N. Carrasco, F. Davoudzadeh, and W. E. Watts, J. Chem. Soc, Perkin Trans 2, 1980, 1520.
J. H. Richards and E. A. Hill, J. Am. Chem. Soc. 1959, 81, 3484.
G. Gerichelli, B. Floris, and G. Ortaggi, J. Organomet. Chem. 1974, 78, 241.
C. Lo Sterzo and G. Ortaggi, Tetrahedron, 1984, 40, 593.
C. A. Bunton, N. Carrasco, and W. E. Watts, J. Organomet. Chem., C, 1977, 131, 21.
L. I. Kazakova, N. M. Loim, E. G. Perevalova, and Z. N. Parnes, J. Org. Chem. USSR (Engl. Transl.), 1974, 2294.
C. A. Bunton, W. E. Watts, Tetrahedron Lett. 1977, 2049.
C. A. Bunton, N. Carrasco, N. Cully, and W. E. Watts, J. Chem. Soc, Perkin Trans. 2, 1980, 1859.
H. Mayr and D. Rau, Chem. Ber. 1994, 127, 2493.
G. Neshvad, R. M. G. Roberts, and J. Silver, J. Organomet. Chem. 1982, 236, 237.
C. Cordier, M. Gruselle, J. Vaissermann, L. L. Troitskaya, V. I. Bakhmutov, V. I. Sokolov, and G. Jauoen, Organometallics, 1992, 11, 3825.
S. Braun, T. S. Abram, and W E. Watts, J. Organomet. Chem. 1975, 97, 429.
U. Behrens, J. Organomet. Chem. 1979, 182, 89.
G. A. Olah, P. W. Westerman, and D. A. Forsyth, J. Am. Chem. Soc. 1975, 97, 3419.
K. V. Kilway and A. Streitwieser, Jr., Abstracts of 213 ACS National Meeting, San Francisco, CA, April 13-17, 1997.
C. A. Bunton and A. Konasiewicz, J. Chem. Soc. 1955, 1354.
C. G. Swain, R. B. Mosely, and D. F. Bown, J. Am. Chem. Soc. 1955, 77, 3731; C. G. Swain, T. E. C. Knee, and A. Maclachlan, J. Am. Chem. Soc. 1960, 82, 6101.
D. N. Kevill and A. R. Pinhas, J. Org. Chem. 1993, 58, 197.
S. Winstein, B. Appel, R. Baker, and A. Diaz, in: Organic Reaction Mechanisms, The Chemical Society, London 1965, pp. 124–126.
A. H. Fainberg and S. Winstein, J. Am. Chem. Soc. 1956, 78, 2770.
T. W. Bentley and P.v. R. Schleyer, J. Am. Chem. Soc. 1976, 98, 7658.
S. Winstein, E. Grunwald, and L. L. Ingraham, J. Am. Chem. Soc. 1948, 70, 821.
S. Ašperger and B. Cetina-Čižmek, in preparation.
D. N. Kevill and S. W. Abderson, J. Am. Chem. Soc. 1986, 108, 1579.
R. S. Drago and D. C. Ferris, J. Phys. Chem. 1995, 99, 6563.
M. J. Weaver, Chem. Rev. 1992, 92, 463, and refs. therein.
G. E. Mc Mannis, R. M. Nielson, A. Gochev, and M. J. Weaver, J. Am. Chem. Soc. 1989, 111, 5533.
R. M. Nielson, G. E. Mc Manis, M. N. Golovin, and M. J. Weaver, J. Phys. Chem. 1988, 92, 3441.
H. Köpf, Anticancer Res. 1986, 6, 33; Arzneim. Forsch. 1987, 37, 532; Eur. J. Cancer Clin. Oncol. 1985, 21, 853.
N. Freestone, Educ. Chem. 1988, 25, 156.
S. E. Sherman and S. J. Lippard, Chem. Rev. 1987, 1153.
A. Pasini and F. Zunino, Angew. Chem., Int. Ed. Engl. 1987, 26, 615.
M. J. S. Dewar and K. M. Merz, J. Am. Chem. Soc. 1987, 109, 6553.
B. K. Keppler and K. Michels, Arzneim. Forsch. 1985, 35, 1837.
P. Köpf-Maier and H. Köpf, Chem. Rev. 1987, 87, 1137.
I. Haiduc and C. Silvestru, Coord. Chem. Rev. 1990, 99, 253–296.
J. C. Ruble and G. C. Fu, J. Org. Chem. 1996, 61, 7230.
E. F. V. Scriven, Chem. Soc. Rev. 1983, 12, 129.
E. Vedejs and X. Chen, J. Am. Chem. Soc. 1996, 118, 1809.
J. C. Ruble, H. A. Latham, and G. C. Fu, J. Am. Chem. Soc. 1997, 119, 1492.
S. Stinson, Chem. Eng. News, 1997 (February 17), p. 10.
A. Togni and T. Hayashi, Eds., Ferrocenes, VCH, New York 1995.
A. Togni, Angew. Chem., Int. Ed. Engl. 1996, 35, 1475.
H. C. L. Abbenhuis, U. Burckhardt, V. Gramlich, A. Martelletti, J. Spencer, I. Steiner, and A. Togni, Organometallics, 1996, 15, 1614.
C. Janiak and H. Schumann, Adv. Organomet. Chem. 1991, 33, 291.
C. J. Pederson, J. Am. Chem. Soc. 1967, 89, 2495.
J. C. Medina, I. Gay, Z. Chen, L. Echegoyen, and G. W. Gokel, J. Am. Chem. Soc. 1991, 113, 365.
J. C. Medina, C. Li, S. G. Bott, J. L. Atwood, and G. W. Gokel, J. Am. Chem. Soc. 1991, 113, 366.
E. C. Constable, Angew. Chem., Int. Ed. Engl. 1991, 30, 407.
J. C. Medina, T. T. Goodnow, M. T. Rojas, J. L. Atwood, B. C. Lynn, E. A. Kaifer, and G. W. Gokel, J. Am. Chem. Soc. 1992, 114, 10583.
P. D. Beer, Z. Chen, M. G. B. Drew, J. Kingston, M. Ogden, and P. Spencer, J. Chem. Soc, Chem. Commun. 1993, 1046, and refs. therein.
Z. Chen, A. R. Graydon, and P. D. Beer, J. Chem. Soc, Faraday Trans. 2, 1996, 97.
B. Dietrich, Pure Appl. Chem. 1993, 65, 1457.
P. D. Beer, Z. Chen, A. J. Goulden, A Grieve, D. Hesek, F. Szemes, and T. Wear, J. Chem. Soc, Chem. Commun. 1994, 1269; P. D. Beer, D. Hesek, J. Hadacovd, and S. E. Stokes, J. Chem. Soc, Chem. Commun. 1992, 270; P. D. Beer, Chem. Soc. Rev. 1989,18, 409.
S. Barlow and D. O’Hare, Chem. Rev. 1997, 97, 637–669.
H. H. Brintzinger, D. Fischer, R. Mülhaupt, B. Rieger, and R. Waymouth, Angew. Chem. 1995, 107, 1255; Angew. Chem., Int. Ed. Engl. 1995, 34, 143; H. Cherdron, M. J. Brekner, and F. Osan, Angew. Macromol. Chem. 1994, 223, 121.
W. A. Herrmann and B. Cornils, Angew. Chem., Int. Ed. Engl. 1997, 36, 1048–1067.
P. Gómez-Elipe, P. M. Macdonald, and I. Manners, Angew. Chem., Int. Ed. Engl. 1997, 7, 762; I. Manners, Adv. Organomet. Chem. 1995, 37, 131; S. Barlow, L. Rohl, S. Shi, C. M. Freeman, and D. O’Hare, J. Am. Chem. Soc. 1996, 118, 7578; R. Rulkens, Y. Ni, and I. Manners, J. Am. Chem. Soc. 1994, 116, 12121; T. J. Peckham, J. A. Massey, M. Edwards, I. Manners, and D. A. Fencher, Macromolecules, 1996, 29, 2396.
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Ašperger, S. (2003). Metallocenes, Strong Electron Donors. In: Chemical Kinetics and Inorganic Reaction Mechanisms. Springer, Boston, MA. https://doi.org/10.1007/978-1-4419-9276-5_10
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