By F Gordon A Stone; Robert West
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Extra info for Advances in organometallic chemistry. / Volume 1
Viewed in this way the decreased electrophilicity of the cation (LXXI) may be ascribed to the large extent of electron transfer from the metal to the ligand via back donation. In line with this is the fact that cationic complexes of this type show abnormally high carbonyl absorption frequencies in the infrared. Recent work by several groups has shown that the d i e n ~ l - F e ( C 0 unit )~ exists as a stable group present in several related cationic species. Thus Dauben and Bertelli (27) have prepared cycloheptadienyl-iron tricarbonyl fluoroborate (LXXII) from ~ycloheptadiene-Fe(C0)~ (XXXIV) and triphenylmethyl fluoroborate.
PETTIT & G. F. EMERSON 28 What appear to be perfl~orodiene-Fe(C0)~ complexes have been obtained from the reaction of perfluorodienes with iron carbonyls. Thus, as indicated in Eq. The latter reaction involves a fluorine shift reminiscent of the hydrogen shift observed in the analogous reaction with 1,4-cyclohexadiene (43). F F (LXVII) The reaction of perfluorobutadiene with Fe3(C0)12has yielded an organoiron complex but its instability has deterred intensive investigation (85). The electronic structures of the perfluorinated diene complexes are no more clear than those of the corresponding hydrocarbon complexes, but it is thought that u bonding might be preferred overz- bonding in these systems.
G. A. Stone, Z. Naturforsch. 17b, 575 (1962). 105. G. W. Parshall and G. Wilkinson,J. Chem. SOC. p. 1132 (1962). 84,118 (1962). 106. C. E. Coffey,J. A m . Chem. SOC. 107. S. F. A. Kettle and L. E. Orgel, Chem. Znd. (London) p. 49 (1960). 108. A. R. Luxmoore and M. R. Truter, Proc. SOC. Chem. p. 466 (1960). 109. A. R. Luxmoore and M. R. Truter, Acta Cryst. 15, 1117 (1962). 110. H. D. Murdoch and E. Weiss, Helv. Chim. Acta 45, 1156 (1962). 111. E. Weiss, K. Stark, J . E. Lancaster, and H. D. Murdoch, Helv.
Advances in organometallic chemistry. / Volume 1 by F Gordon A Stone; Robert West