3553
Macro Rings. XL. Transannular Interactions in the Tetracyanoethylene Complexes of [ 3.31Paracyclophane and Derivatives' Michael Sheehan and Donald J. Cram Contribution No. 2298 from The Department of Chemistry of The University of California at Los Angeles, Los Angeles, California 90024. Received December 20. 1968 Abstract: Equilibrium constants for 1 : 1 a-salt formation between tetracyanoethylene and [3.3]-, [3.4]-, [2.2]-, [leg]-,[9]-, [4.4]-, and [6.6]paracyclophane were found to decrease in value in the order listed, the values being higher than that for the open-chain model compound, 1,3-bis(4-ethylphenyl)propane. A rough linear correlation between the equilibrium constants and the position of the A,, of the long-wavelength charge-transfer band in the visible spectrum of the r-salts has been observed for these and four monosubstituted [2.2]paracyclophanes. An exception to the correlation was the r-salt of [4.4]paracyclophane. The positions of A,, values of the long-wavelength chargetransfer band of the r-salts of 13 substituted [3.3]paracyclophanes were determined. Possible correlations between AEt's (differences in electronic transition energies between the 5-substituted [3.3]paracyclophanes and [3.3lparacyclophane itself) and substituent constants were examined. A rough linear correlation was observed between AEt values and um constants for the electron-withdrawing substituents. The nonsubstituted ring was the more basic of the two, and was probably the main site of salt formation. This correlation demonstrates the presence of transannular electronic effects in the [3,3]paracyclophane system. Comparison of the slope of the plot for the [3.31paracyclophane derivatives with the formerly determined slope of the plot for the [2,2]paracyclophane derivatives demonstrated the transannular effects in the latter system to be greater. An even poorer linear correlation was observed between AEt of a-salts of [3.3]paracyclophane substituted with electron-providing groups and UA+ (r = 0.25) values. From its AEt value the acetamido substituent appeared to function as a moderately strong electron-withdrawing group when attached to [3,3]paracyclophane, whereas its cm value indicates that the group should be a weak electron donor. This abnormal behavior was also observed for 5-acetamido[3.4]paracyclophane,but not for 4-acetamido[2.2]paracyclophane. The 1:1 tetracyanoethylene-[3.3]paracyclophane salt was prepared in a crystalline form and analyzed.
T
he formation of stable ir-a-salts between tetracyanoethylene2 (TCNE) and the [m.n]paracyclop h a n e provided ~~~ a simple means of investigating the change in the ir-base strength of the aromatic hydrocarbons with changes in values of m and n,3a and with changes in substituents on the aromatic nucleus of [2.2]para~yclophane.~~ The relative basicities of the KC,
c
,CN
t etracyanoethylene a-acid
[m. nlparacyclophane 7r
base
a-7r
salt
cycles were estimated making use of the transition energies (Et's) of the long-wavelength charge-transfer bands in the visible absorption spectra of the a-a-salts. Results of Merrifield and Phillips4 established a correlation between the equilibrium constant ( K ) for ir-asalt formation between methylbenzenes and T C N E and the A, of the charge-transfer band of the salt. Application of this correlation to include the [m.n]paracyclophanes led to the a-base order [3.3]- > [3.4]- > [2.2]- > [6.6]- > [4.4]para~yclophane.~"Application of the correlation to 4-substituted [2.2]paracyclophanes demonstrated that electron-withdrawing substituents in one benzene ring deactivated the other ring toward salt formation. The objective of the present study was twofold: to establish the 7r-base orders of the paracyclophane hydrocarbons by determination of the equilibrium constants with TCNE; to compare the importance of transannular effects on T basicity of the 5-substituted [3.3]paracyclophanes (IV) with those of the 4-substituted [2.2]paracyclophanes (V). The two parent hydrocarbon systems possess geometries that differ in important respects as revealed by their X-ray crystal
n
(1) The authors wish to thank the National Science Foundation for a grant used in support of this research. M. S . also wishes to thank the
National Science Foundation for a National Science Foundation Predoctoral Fellowship, 1965-1969. (2) T. L. Cairns, R. A. Carboni, D. D. Coffman, V. A. Engelhardt, R. E. Heckert, E. L. Little, E. G. McGeer, B. C. McKusick, W. J. Middleton, R. M. Scoibner, C. W. Theobald, and H. E. Winberg, J . Am. Chem. Soc., 80,2775 (1958) (3) (a) D J. Cram and R. H. Bauer, ibid., 81, 5971 (1959); (b) L. A. Singer and D. J. Cram, ibid., 85, 1080 (1963).
U 5-Xr3.31paracyclophane (IV)
U 4 - X k 21 paracyclophane (V)
(4) R. E. Merrifield and W. D. Phillips, ibid., 80,2778 (1958).
Sheehan, Cram 1 Tetracyanoethylene Complexes of [3.3]Paracyclophanes
3554 structures.5 In [2.2]paracyclophane the four methylene carbons and the aromatic carbons to which they are attached all occupy the same plane, and the two benzene rings are centered. In [3.3]paracyclophane the six methylene carbons describe an elongated chair (or chaise lounge), and the two benzeneorings are displaced from a center$d position by 0.19 A along the longer axis and 0.44 A along the shorter axis of the molecule. As expected, [2,2]paracyclophanepossesses considerable strain energy, which combustion indicates to be 31.3 kcal/mol.ea The strain energy of [3,3]paracyclophane has been calculated5' to be about 7 kcal/mol, and combustion indicates it to be 12 kcal/mol.eb
I
I1
Crystal structure of
Crystal structure of
[2,2Jpsracyclophane
[~.31paracyc~ophane 113.6' 116.8'
of (A)l/log ( l o / Z ) us. I/[paracyclophane] gave good straight lines whose slopes provided the equilibrium constants of Table I. The values for K and E for the Table I. Correlation between Equilibrium Constants ( K of TCNE Hydrocarbon e T-n-Salts) and Longest Wavelength Charge-Transfer Bands in the Visible Spectrum in Dichloromethane at 25" of the s-r-Salts
+
A,,
Hydrocarbon
K
79 f 12 52 f 2 42 19 j=2 16 f 4 13 1 36 f 1 13 + 2 52 4-Ethyl[2.2]paracyclophane~ 4-Acetyl[2.2]paracyclophanec 24.5 8 4-Cyano[2.2]paracyclophanec 263 Hexamethylbenzened 123 Pentamethylbenzened 54.2 Durened 17.3 Mesitylened 7.6 o-XYlened [3.3]Paracyclophanea [ 3,4]Paracyclophanea [2.2]Paracyclophaneb [ 1.9lParacyclophane" [9]Paracy clop hane" [6.6]Paracyclophanea [4.4]Paracyclophanea 1,3-Bis(4-ethylphenyl)propaneQ
+
mg
599 538 521 509 492 490 476 477 540
496 475 545 520 480 461 460
E,
I. cm-l mol-'
1800 f 300 1900 + 100 1720 & lOOO+ 2690 2 1650 2 1180+ 1610 1450 2000 4390 3270 2075 3120 2650
150 200 100 50 150
0 Values for K and E determined by least-squares analysis. K taken from ref 10. c Data taken from ref 3b. Data taken from ref 4.
1.382
111 Crystal structure of [3.3] paracyclophane
Results Starting Materials. From previous investigations samples were available of [2.2]-,7" [3.3]-,7b [3.4]-,'" [4.4]-,7d[6.6]-," [ 1.9]-,7fand [9]para~yclophane,~g as well as the open-chain model compound, 1,3-bis(4-ethylphenyl)pr~pane.~"A sample of [8]paracyclophane was prepared as before,8a and the 5-substituted [3.3]paracyclophanes were available from a prior study.*b Equilibrium Constants. Equilibrium constants in dichloromethane between one molecule of TCNE and one molecule of each paracyclophane on the one hand and the A-malts on the other were measured as previously described3b making use of the BenesiHildebrand equationg (1). In this equation (A) is the initial concentration of the A-acid, [D] is the initial mole fraction of r-base, I is the light path in centimeters, E is the apparent molar extinction coefficient of the charge-transfer band of the A-malt, lo/l is the absorbance of the mixture, and K is the equilibrium constant. Equation 1 holds only for the condition that [D] >>
+
(A)l/log ( l o / l ) = l/Ke[D] [DA], where [DA] is the mole fraction r-r-salt.
(1) Plots
( 5 ) (a) C. J . Brown, J . Chem. Soc., 3265 (1953); (b) P. Gantzel, C. L. Coulter, and I
