Abstract
An alternative structure for ferrocene is proposed on the basis of the isolobal analogy. Its bonding and stability relative to the classical structure of ferrocene has been examined by extended Hückel and ab initio calculations. Extension to other metallocenes and a strategy to stabilize this nonclassical type of structure has been carried out.
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a) T.J. Kealy and P.L. Pauson, Nature, 168, 1039 (1951). b) G. Wilkinson, M. Rosenblum, M.C. WhvtThg and R.B. Woodward, J. Am. Chem. Soc, 74, 2125(1952). c) R.B. Woodward, M. Rosenblum, and M.C. Whiting, ibid, 74, 3458 (1952).
A perhaps typical reaction to this discovery may be found in A.S. Smith, Chem. Ind., 353 (1955).
a) C.M. Lukehart, “Fundamental Transition Metal Organometallic Chemistry” Books/Cole, Belmont, CA (1985). b) J.P. Collman and L.S. Hegedus, “Principles and Applications of Organotransition Metal Chemistry”, University Science Books, Mill Valley, CA (1980). c) M. Tsutsui, M.N. Levy, A. Nakamura, M. Ichikawa, and K. Mori, “Introduction to Metal π-Complex Chemistry”, Plenum Press, New York, NY (1970). d) G. Deganello, “Transition Metal Complexes of Cyclic Polyole-fins”, Academic Press, New York, NY (1979).
a) R. Hoffmann, Angew. Chem., 94, 725(1982); Angew. Chem., Int. Ed. Engl., 21, 711(1982). b) T.A. Albright, J.K. Burdett and M.-H. Whangbo, “Orbital Interactions in Chemistry”, John Wiley, New York, NY (1985). c) T.A. Albright, Tetrahedron, 38, 1339(1982).
a) M. Rosenblum and B. North, J. Am. Chem. Soc., 90, 1060(1968). b) M. Rosenblum, B. North, D. Wells, and W.P. Giering, ibid, 94, 1239(1972). c) M. Rosenblum, W.P. Giering, B. North, and D. Wells, J. Organomet. Chem., 28, C17(1971). d) W.S. Lee and H.H. Brintzinger, ibid, 127, 93(1977).
H. Hogeveen and P.W. Kwant, Accts. Chem. Res., 8, 413(1975); H. Carnadi, C. Giordano, R.F. Heldeweg, H. Hogeveen, and E.M.G.A. van Kruchten, Isr. J. Chem., 21, 229(1981); H. Hogeveen and E.M.G.A. van Kruchten, J. Org. Chem., 46, 1350(1981).
D.W. Thorn and R. Hoffmann, Inorg. Chem., 17, 126 (1978).
E.M. Shustorovich and M.E. Dyatkina, Doklady Akad. Nauk. SSSR, 128, 1234 (1959); O.Ya. Lopatko, N.M. Klimenko, and M.E. Dyatkina, ibid, 192, 1083(1970); M.-M. Rohmer and A. Veillard, Chem. Phys., 11, 349 (1975); P.S. Bogus, U.E. Walgren, and J. Almlof, J. Chem. Phys., 64, 2324(1976).
H.T. Jonkman and W.C. Nieuwpoort, Tetrahedron Lett., 1671 (1971); E.D. Jemmis and P.V.R. Schleyer, J. Am. Chem. Soc., 104, 4781(1982); K. Lammertsma and P.V.R. Schleyer, ibid, 105, 1049(19837); V.I. Minkin and R.M. Minyaev, Usp. Khim., 51, 586 (1982) M.J.S. Dewar and M.K. Holloway, J. Am. Chem. Soc, 106, 6619(1984).
C. Kruger, B.L. Barnet, and D. Brauer in “The Organic Chemistry of Iron” Vol. 1, E.A. Koerner von Gustorf, F.-W. Grevels, and I. Fischler, eds., Academic Press, New York, NY (1978), pp. 1–112.
M. Elian, M.M.L. Chen, D.M.P. Mingos, and R. Hoffmann, Inorg. Chem., 15, 1148(1976).
D.L. Thorn and R. Hoffmann, Nouv. J. Chim., 3, 39(1979).
J. Silvestre, PhD Dissertation University of Houston (1983).
W.J. Pietro and W.J. Hehre, J. Comput. Chem., 4, 241(1983).
R. Hoffmann, S. Swaminathan, B.G. Odell, and R. Gleiter, J. Am. Chem. Soc., 92, 7091(1970).
H.P. Luthi, J.H. Ammeter, J. Almlof, and K. Korsell, Chem. Phys. Letts., 69, 540(1980); H.P. Luthi, J.H. Ammeter, J. Almlof, and K. Faegri, J.Chem. Phys., 77, 2002(1982); J. Almlof, K. Faegri, B.E.R. Schilling and H.P. Luthi, Chem. Phys. Letts., 106, 266(1984); T.E. Taylor and M.B. Hall, ibid, 114, 338 (1985).
For reviews see, G.E. Herberich in “Comprehensive Organometallic Chemistry”, G. Wilkinson, F.G.A. Stone, and E.W. Abel, eds., Vol. 1, Pergamon Press, Oxford (1982), pp. 381–410; K.H. Pannell, B.L. Kalsotra, and C. Parkanyi, J. Heterocyclic Chem., 15, 1057 (1978).
A. Efraty, Chem. Rev., 77, 691(1977); G.M. Reissner, I. Bernai,. M.D. Rausch, S.A. Gardner, and A. Clearfield, J. Organomet. Chem., 184, 237(1980); P.E. Riley and R.E. Davis, Organometallics, 2, 286 (1983) and references therein.
R. Case, E.R.H. Jones, N.V. Schwartz, and M.C. Whiting, Proc. Chem. Soc., 256(1962); see also M.E.E. Veldman, H.R. vanderWal, S.J. Veenstra, and H.J. DeLiefde, J. Organomet. Chem., 197, 59(1980) for a related example.
M. Mlekuz, P. Bougeard, B.G. Sayer, S. Peng, M.J. McGlinchey, A. Marinetti, J.-Y. Saillard, J.B. Naceur, B. Mentzen, and G. Jaouen, Organometallics, 4, 1123(1985).
H. Hoberg, R. Krause-Going, C. Kruger, and J.C. Sekutowski, Angew. Chem., 89, 179(1977); Angew. Chem. Int. Ed. Engl., 16, 183(1977).
T.P. Fehlner, J. Am. Chem. Soc., 100, 3250(1978).
V.R. Miller and R.N. Grimes, ibid, 95, 5079(1973); 97, 4213(1975); D.C. Beer, V.R. Miller, L.G. Sneddon, R.N. Grimes, M. Mathew, and G.J. Palenik, ibid, 95, 3046(1973); R.Weiss and R.N. Grimes, ibid, 99, 8087(1977) Inorg. Chem., 18, 3291(1979); W.T. Robinson and R.N. Grimes, ibid, 14, 3056(1975); R.N. Grimes, E. Sinn, and R.B. Maynard, ibid, 19, 2384(1980); L.G. Sneddon and D. Voet, J. Chem. Soc, Chem. Commun., 118(1976); V.R. Miller, R. Weiss, and R.N. Grimes, J. Am. Chem. Soc., 99, 5646(1977).
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Albright, T.A., Lopez, J.P., Silvestre, J. (1986). Molecular Orbital Calculations on Metallocenes with Unusual Geometries. In: Veillard, A. (eds) Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. NATO ASI Series, vol 176. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-4656-9_24
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DOI: https://doi.org/10.1007/978-94-009-4656-9_24
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