The Electronic Properties of Fluoroalkyl Groups. Fluorine p-7~ Interaction’ William A. Sheppard Contribution No. 1039 f r o m the Central Research Department, Experimental Station, E. I . du Pont de Nemours and Company, Wilmington 98, Delaware. Received January 22, 1965 The inductive and resonance efects of the pentafluoroethyl, nonafluoro-n-butyl, and heptafluoroisopropyl groups determined f r o m p K , measurements on benzoic acids and anilines are similar to those of a tri3uoromethyl group. These results are discussed in terms of fluoride ion hyperconjugation and n-inductive e f e c t , and a new explanation is proposed f o r the + R character of the fluoroalkyl groups. The interaction of p-electrons of the fluorines with the w-system of the aromatic ring causes signijcant return of electron density to the ring, partly counteracting the normal strong inductive withdrawal. This effect is more important at the meta than the para position so that the para position appears more strongly deactivuted. This hypothesis is strongly supported b y a discussion of u-parameters f o r other fluorinated groups, such as C(OH)(CF,),, N(CF3)2, and SF5, and a new approach to interpretation of F19 chemical shift correlations with subhtituent parameters f o r benzotrijuorides and arylsulfur pentafluorides.
The strongly deactivating effect of the trifluoromethyl group is well recognized. Quantitative measurements have shown that this effect can be mainly attributed to an inductive withdrawal, but in aromatic systems a significant enhancement by a conjugative contribution (fR character) is also found., Mutual interactions of the nitro or cyano type are not possible, and two other mechanisms have been proposed to explain the + R effect of a trifluoromethyl g r o ~ p . ’ ~ , ~ , ~ A . Fluoride ion hyperconjugation is as represented by the following resonance pictures.
F I
F- C -F
F 1
F-C F
F
-
I
F-C F
-
B. T-Inductive effects result where the strong inductive withdrawal of electrons from the neighboring position o n the ring is transmitted by normal resonance mechanism to the ortho and para position. ( I ) This work was presented in part a t the 19th International Congress of Pure and Applied Chemistry, London, England, July 1963 (see Angew. Chem., 75, 1033 (1963)), and at the 148th National Meeting of the American Chemical Society, Chicago, Ill., Sept. 1964. (2) (a) J. D. Roberts, R. L. Webb, and E. A. McElhill, J . A m . Chem. SOC.,72, 408 (1950); (b) H. van Bekkum, P. E. Verkade, and B. M . Wepster, Rec. Truv. Chim., 78, 815 (1959). (3) M . J. S. Dewar, “Hyperconjugation,” The Ronald Press Co., New York, N. Y . , 1962, p. 159. (4) A. Streitwieser, Jr., and H. F . Koch, J . Am. Chem. Soc., 86, 404 (1964).
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Journal of the American Chemical Society
Q The fluoride ion hyperconjugation mechanism has also been proposed for stabilization of carbanions5 and in a “double bond-no bond resonance” picture6 to explain the stability of polyfluorides of methane. Neither of the above mechanisms is satisfactory in explaining all pertinent data, and pro and con arguments have been presented. In addition to the general arguments against the hyperconjugation mechanism,, we have noted that the f R effect for the S F j group is similar in size to that of the trifluoromethyl.’ This similarity suggests that the + R effect has a common origin, which is considered unlikely to result from hyperconjugation because of the gross differences between C F and S F bonds. On the other hand, the T inductive effect does not explain why urnis the same as c$ for the +N(CH3), group8 without invoking a special field effect from the positive ~ h a r g e . ~The recent report that u, and no are both 1.3 for an electrically neutral lC12 groupg cannot be explained by this theory. To obtain new experimental results that could resolve this mechanistic question, we undertook t o determine the change, if any, in resonance effect that resulted by replacing the fluorines of the C F , group with perfluoroalkyl groups. As pointed out previously,1° the inductive effect of F and C F 3 are almost the same. Consequently we predicted that for the T-inductive mechanism n o significant change in resonance effect should occur in going from C F , to C(CF3),, but for the hyperconjugation mechanism, the + R effect should drop significantly. l 1 In any case, quantitative comparison of the electrical effect of a series of fluoroalkyl groups is of value to gain a better insight into the effects of fluorine substitution. Recent synthetic developments made possible preparation of a series of fluoroalkyl aromatics that could be employed for the classical measui ement of pK, and dipole moments’s3 as well as the recently developed technique of F19 n.m.r. chemical shift correlation^.^^ l 2 In particular, the use of sulfur t e t r a f l ~ o r i d e ’for ~ con( 5 ) S . Andreades, ibid., 86, 2003 (1964). (6) J. Hine, ibid., 85, 3239 (1963). (7) W. A. Sheppard, ibid., 84, 3072 (1962). (8) J. D. Roberts, R . A. Clement, and J. J . Drysdale, ibid., 73, 2181 (1951). (9) G.A. Maciel, ibid., 86, 1269 (1964). (IO) W. A. Sheppard, ibid., 85, 1314 (1963). ( 1 I ) One difficulty in this approach is the argument that the hyperconjugation effect of a -CF3 could be as effective as -F. (12) R . W. Taft, E. Price, I. R. Fox, I. C. Lewis, I
