Proc. Nati. Acad. Sci. USA Vol. 78, No. 4, pp.

1998-2002, April 1981 Chemistry

'3C NMR chemical shift correlations in application of "tool of increasing electron demand" to stable long-lived carbocations: Comprehensive evaluation*
(stable carbocations/chemical shift-substituent constant relationships/onset of nonclassical gr delocalization)

GEORGE A. OLAH, ARTHUR L. BERRIER, AND G. K. SURYA PRAKASH

Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90007

Contributed by George A. Olah, October 20, 1980

ABSTRACT The reliability of "3C NMR chemical shift correlations in the application of the "tool of increasing electron demand" to stable long-lived carbocationic systems is demonstrated by a comprehensive analysis of 22 stable aryl-substituted carbocationic systems. The observation of slopes of less than unity in such chemical shift correlations for several cationic systems has been attributed to additional charge delocalizing mechanisms present in the system (such as homoallylic, cyclopropyl, and ir conjugations). The onset of nonclassical or-delocalization in 2-aryl2-norbornyl cations with electron withdrawing-substituents previously observed was further verified by using ac+ substituent constants. Difficulties in relating the CaNMR shifts in different carbocationic systems are also discussed.
In recent years considerable effort was expended in explaining and predicting the effects of substituents on various physical properties, equilibria, structures, and reactivities of organic molecules (2-8). These effects can be broadly divided into electronic and steric components. For probing electronic effects the so-called tool of increasing electron demand is frequently utilized. Although it is only one of the many methods to probe into the nature of electron-deficient intermediates, recently there has been an upsurge in its applications in both stable ion (9-12) and solvolytic studies (13). The ability of this method to detect the onset of of or Xi participation or conjugation in many carbocationic systems makes it a useful tool in determining the nature of carbocationic intermediates. In stable ion studies the method is generally applied by using '3C NMR chemical shifts as the structural probe (9-12) although 1H and '9F chemical shifts have also been used (14-16). It is well understood that 13C NMR chemical shifts cannot be directly equated to charge densities. However, in closely related homologous carbocations of similar nature, there is considerable cancellation of factors other than charge distribution that enter into the makeup of the chemical shifts. Based on this assumption Farnum et al. (10, 17) and Olah etal. (9, 11, 12) have applied the tool of increasing electron demand to a wide variety of aryl-substituted carbocations, using 13C NMR spectroscopy as the structural probe. The method was successful in demonstrating the clearly different nature of certain carbocationic systems such as the 7-norbornenyl (9), 5-norbornene-2-yl (2) (10), 2-norbornyl (3) (10, 11) and 8-tricyclo[5.2. 1.02'6]decyl (4) (10) cations compared to ordinary trivalent (classical) cations. Such 13C NMR chemical shift comparisons have been criticized by Brown and Rao (18) and by Kelly and Spear (19). In this paper we demonstrate that such comparisons are of general validity.
The publication costs of this article were defrayed in part by page charge payment. This article must therefore be hereby marked "advertisement" in accordance with 18 U. S. C. 1734 solely to indicate this fact.
1998

RESULTS AND DISCUSSION The 13C NMR data of various aryl-substituted carbocations are listed in Tables 1 and 2 (9, 10, 12, 20, 21). New data on the 2adamantyl system are also presented. Table 3 lists the slopes of 13C NMR chemical shift plots. In the case of carbocations displaying nonlinear plots, the slopes were determined only with the substituents over which the carbocations displayed linear behavior. Figs. 1, 2, and 3 show plots of the cationic center chemical shifts with either oc' (20) or r (4) substituent constants. Correlation of 13C NMR Chemical Shifts (Nature of the Slopes). Recently, attempts to relate r constants and groundstate physical properties (such as 'H, '9F, and 13C NMR chemical shifts) obtained under stable ion conditions have been published. However, these ea constants were derived from solR

18

+a

18

18

/CH3

~"CH,L..J+
10
11

R8

12

13

/R

,/CH,
15

N-/R
C

HC -C
14

14

\ \ -> 1 L- C CH1CH,
16

C C,
17

/H

C\
18
R
=

>

C\

R-C

8 -C

CH,
20 21

19 -X

X=4-OCH3, 4-CH3, 3,4(CH3)2, 4-F. 4-Cl. 4-Br, 4-H, 3-CH,, 3-F, 3-Cl. 4-CF3, and 3,5(CF3)2

This paper is part 233 in the series "Stable Carbocations." Part 232 is ref. 1.

Chemistry: Olah et al.

Table 1. Cationic chemical shifts of carbocations studied

Proc. Natl. Acad. Sci. USA 78 (1981)

1999

Shifts with aryl substituents

Cation 12 11 1 22 10
9 8 7 6 3 5 4 13 16 15 19 18 21 20 2

Ref. 9 20 9 19
10 10

4-OCH3 3,4(CH3)2 4-CH3 234.6 259.5 219.0 243.6 229.9 252.5 196.3 219.1
227 235 237.5 235.5 213.6 232 231.4 231.9 235.0 231.0 227.1 208.6 183.5 219.8 248.7 226.8

4-F
-

4-Cl
-

4-Br
-

3-CH3
269.7

248.4
-

251.4
-

252.3
-

253.3
-

223.4
256 264
-

225.7
259 267
-

226.1
260 267
-

249 257
-

10 12 10 9 10 9 21 21 21 22 21 21 10

256.4 251.5 250.4 -

251 259 260.7 234.3 252.4

-

268.3t
-

4-H 271.7 255.7 263.9 229.8 263

270 271.3 268.6

3-F
-

3-Cl
-

262.1
-

262.3
-

267
277
-

4-CF3 3,5(CF3)2 285.3* 290.1t 270.0 274.4 277.8 283.1 244.1 248.8 276 279
283 283.4 279.5

277
-

251.1 246.1 241.9 221.6 196.1 231.5 257.0

-

262.3 255.8 255.0 247.8 243.2 222.2 197.1 232.5 258.0

-

265.4
-

258.5
258.2 250.6 245.3 223.6 198.1 233.5 260.0
-

245.1 260.8
261.3 260.4 257.1 251.6 246.2 226.3 199.8 235.0 261.0 247.4

286 287.1 282.2

256.5
-

249.4 244.8 223.1 197.8 233.4 259.8

-

254.4 265.3 272.5 268.0 260.5 254.8 250.0 225.9 202.2

235.3 264.6 234.4

258.2 263.3 275.2 268.4

259.0 -

242.6

218.1

t At - 123.40C. t Measured in FSO3H/SbF5/SO2ClF at - 700C for this study.

*At - 1140C.

volytic studies (4) and do not properly reflect the greater electron demand of carbocations in non-nucleophilic superacid media. Indeed, it has been shown (19) that a plot of the `3C NMR chemical shifts of the cationic carbon in a series of substituted t-cumyl cations 11 against the a- constants reveals a poor correlation. "Super sigma" constants, 0A', have been derived by Kelly and Spear (19) to take into account the enhanced charge delocalization in ions containing electron-donating substituents. However, the method used in deriving these constants assumes a linear correlation between the cationic chemical shift and o+ values for electron-withdrawing substituents. Farnum et al. (10) observed that the 13C NMR chemical shifts of the cationic carbons of ordinary tertiary-aryl-substituted classical ions are linearly related to one another with nearly unit slope. This finding has been exploited in recent studies establishing the extraordinary behavior of several carbocationic systems (9, 10). However, we have observed that the slopes in several instances fall substantially below the unity level observed previously. For example, the slope of the plot of the cationic carbons of 1-aryl-l-cyclopentyl 9 (10) and 2-aryl-2bicyclo[2. 1. 1]hexyl 5 cations (9) was 0.85, lower than the usually observed values of 1 0.1. Even more striking was the slope of the 3-aryl-3-nortricyclyl cations 13 (9). A plot of the cationic (C-3) chemical shifts of these cations versus those of the model l-aryl-l-cyclopentyl cations (10) reveals a deviation for electronwithdrawing groups due to increased cyclopropyl conjugation. However, a linear plot is observed for the electron-donating substituents with a slope ofonly 0.63, considerably less than the expected unity. One previous observation of a decreased slope was made by Farnum et al. (10) in the case of the 1, 1-diarylethyl cation 14, in which a slope of 0.71 was found. In order to understand this phenomenon further, we have measured the slopes of the cationic chemical shift plots of various cationic systems with the model-l-aryl-l-cyclopentyl system. These values are listed in Table 3. The slopes of various alkyl-substituted cations such as the 1aryl-l-cyclobutyl 12 (9), 2-aryl-2-adamantyl 8, and 7-aryl-7-norbornyl 1 (9) all fall close to unity. They range from 1.08 in the case of cyclobutyl to 0.97 for 2-adamantyl. This indicates that

these cations behave similarly to the model system 9 (10). Slopes considerably less than unity can be attributed to the presence of an additional charge delocalizing mechanism such as the interaction of either a cyclopropyl group or a phenyl ring with the electron-deficient carbocationic center. The presence of either a cyclopropyl or phenyl substituent causes a substantial decrease in the slope (0.64 or less). The alkyl-substituted cyclopropyl phenyl cations (methyl 15 and ethyl 16) show similiar slopes (0.55 and 0.59, respectively), indicating that these ions involve stabilization by the cyclopropyl group approximately to the same extent. Replacing the alkyl group by hydrogen causes a marked decrease in slope (0.48), indicating increased cyclopropyl conjugation. This observation is expected because the alkyl group (methyl or ethyl) should help stabilize the carbocationic center, resulting in less demand on the cyclopropyl ring. However, the presence of a hydrogen should destabilize the system, causing an increase in the involvement of the cyclopropyl group with a resultant decrease in the slope. The same trend is also observed in the case of the phenyl-substituted cations in which replacement of a methyl group (cation 17) by hydrogen (cation 18) causes a decrease in slope from 0.58 to 0.46. Furthermore, the substitution of additional conjugative stabilizing groups results in a further decrease in slope. The arylphenylcyclopropyl and aryldicyclopropyl cations, 21 and 22, have the smallest slopes observed for classical systems (0.43 and
It is interesting to note that a series of five bicyclic (tricyclic) systems, 3, 4, 5, 6, and 7, all have similiar slopes which are somewhat lower than other simple alkyl-substituted systems (0.92 to 0.81). Although structurely and electronically different, these systems appear to have similiar carbocationic environments as indicated by their slopes. This similarity of slope may be due to an anisotropy effect of the bicyclic skeleton. A analogous bicyclic system is the homoallylic 2-aryl-5-norbornene-2-yl cation 2 previously studied by Farnum et al. (10, 17). A substantial deviation in the chemical shift correlation plot was accommodated as due to either equilibrium 2 = 2b or ir bridging (10). The slope of the line with electron-releasing substituents only, for which a reasonable correlation is obtained

0.34, respectively).

2000

Chemistry:

Olah et al.

Proc. Nati. Acad. Sci. USA 78 (1981)

Chemical shift 4-H 4-CF3 4-N+(CH3)2H 4-Br 3-Me 65.5 58.3 59.3* 63.6 264.6 258.8 260.5* 264.5 53.2 49.8 50.5* 51.9 65.0 70.0 261.3 272.5 46.3 49.4 55.7 59.1 55.2 55.9 268.6 279.5 262.3 265.4 49.6 52.5 49.1 49.6 54.3 56.9 245.1 254.4 46.9 49.1 62.4 63.6 63.2 67.6 255.0 258.2 260.4 268.0 50.6 49.9 50.9 53.2 59.9 61.4 73.5 256.5 257.1 260.5 51.4 56.7 271.3 283.4 49.3 52.8 30.7 29.5 37.0 36.3 137.1 139.5 138.1 137.7 132.9 129.4 154.2 149.2
4-F

Table 2. Additional "3C NMR chemical shifts of selected carbocations

Cation 3
5

Ref. 11
9

4-OCHq
C-1 C-2 C-3 C-1 C-2 C-3 C-5 C-6 C-7 C-1 C-2 C-3 C-1 C-2 C-3 C-1,6 C-3 C-1,3 C-2 C4,8,9,10 C-5,7 C-6 Ci Co 52.0 238.3 45.6 59.5 231.4 42.8 49.8 235.5 44.5 49.3 213.6 42.5 56.3 231.9 45.4 43.4 235.0
44.7 237.5 45.2 28.8 36.2 130.0 142.7 119.9 182.7

3,4(CH3)2
-

4-Me 56.3 252.3 48.6 63.3 252.4 45.6

-

3,5(CF3)2
66.2 262.8 52.4 72.5 275.2 50.5 60.8 282.2 53.6 58.0 258.2 50.0 69.5 268.4 54.1 80.5 259.0 58.6 287.1
54.3 31.0 37.1 142.5

7 6 4 13
8

10
12

53.1 256.4 47.5

-

52.2 234.3 45.3

-

10
9

60.2 250.4 48.6

-

Cm Cp
C'

54.7 251.1 49.1 260.7 48.0 29.4 36.4 135.1 138.7 134.3 173.0

135.8

136.0(36)t
137.9

(33.9)t
59.4

24.6

122.2 (233)t

122.9(272.9)t

* Chemical shifts obtained in FSO3H/SbF5 (4:1)/SO2ClF at -600C forthis study. The C-2 chemical shift is slightly different from previously reported data (11). t JCF coupling constant in Hz.
-=+

Ar

2b

Ar

(r = 0.977), is 0.61 which is definitely lower than the slope of the other bicyclic systems. The presence of homoallylic conjugation, even with electron-releasing aryl substituents, is clearly evident from the magnitude of the slope. Substituent Constant-13C NMR Chemical Shift Relationships. Utilizing the approach previously used in determining or constants, Brown et al. (20) developed orC+ substituent constants which is claimed to take into account the increased electron demand of carbocations in superacidic media. These al+
constants were derived from the cationic carbon chemical shifts of a series of meta- and para-substituted t-cumyl cations using

Hammett-Brown equation. Because these 0.C+ cona linear relationship with the '3C NMR chemical shifts of the cationic carbons of the 1-aryl-l-cyclopentyl cations (20), this approach is essentially an extension of the work of Farnum et al. (10) and Olah et al. (9). The correlation coefficients of plots crC+ and the cationic carbon chemical shifts for a number of reported trivalent aryl substituted cations all show excellent linear relationships, as do plots with the model 1-aryl-l-cyclopentyl system 9. Although the new aG+ substituent constants do not convey
a modified

electron demand fails to reveal any onset of a participation. A plot of the oyC+ constants versus the previously reported (11) carbocationic chemical shifts of the 2-aryl-2-norbomyl cations is shown in Fig. 1. In contrast to the linear plots observed with classical ions, the plot shows a distinct break with the electronwithdrawing 4-trifluoromethyl and 3,5-bistrifluoromethyl substituents. This is consistent with the previous analysis by Farnum et al. (10) ofthe 2-aryl-2-norbomyl cation in which they observed an identical deviation in the plot of the model 6-aryl6-bicyclo[3.2. lioctyl system and the 2-aryl-2-norbornyl cations. Thus, the application of the new o+ constants of Brown et al. (20) further verifies the onset of nonclassical af delocalization in the 2-aryl-2-norbornyl cations. A similar onset of oa delocalization (10) in the 8-aryl-8-tricyclo[5.2. 1.02'6]decyl cations 4 is shown in a plot of the cationic chemical shifts (10) and the a constants (Fig. 2). The onset of of delocalization in the 2-aryl-2-norbornyl cation
occurs with the electron-withdrawing 4-trifluoromethyl and 3,5-bistrifluoromethyl substituents. However, these conclusions have been disputed by Kelly and Spear (19) who questioned the validity of the a+ and C(l) chemical shift plot in which a deviation was found and interpreted in terms of oa delocalization (11). We agree that such cr+ correlation plots are inconclu-

stants show

purely classical systems in which there is no onset of either aor ir participation. The criticism (19) of the C(l) versus C(3) plot which likewise shows a deviation with electron-withdrawing groups, however, is unjustified. The plot (10, 11) shows a distinct break in the curve between electron-releasing and electron-withdrawing

sive because similiar deviations have been found in numerous

thought that the application of these crC+ constants to the controversial 2-norbomyl cation would be appropriate because Brown and Rao (18) have stated that, under solvolytic conditions, the tool of increasing
any new or

unexpected information,

we

Chemistry: Olah et al.

Table 3. Slope of cationic chemical shift vs. SC-1 of 1-aryl-1cyclopentyl cations No. of Cation r points Slope Ref.
12 11 1 22 10 8 7 3 6 5 4 14 13 2 16 17 15 19 18 21 20
*

Proc. Natl. Acad. Sci. USA 78 (1981)

270 265 260 4-H 1 4-Br '

2001

4 3,5-(CF3)2

4-CF3

1.08 1.07 1.03 1.02 1.01 0.97 0.92 0.88* 0.87 0.86 0.81* 0.71 0.64* 0.61* 0.59* 0.58* 0.55* 0.48 0.46* 0.43* 0.34

0.999 0.997 0.997 0.993 0.998 0.999 0.999 0.999 0.998 0.999 0.999 0.998 0.998 0.977 0.995 0.996 0.992 0.988 0.987 0.989 0.994

5 10 5 8 10 5 7 5 5 5 5 4 4 3 6 6 6 6 6 6 7

9 20 9 19 10

255
X 250245 240 235
-

4-F'

10 10 12 9 10 10 9 10 21 10 21 21 22 21 21

4-OCH3
-2.0

-1.5 -1.0

-0.5 arcI

0.0

0.5

1.0

tricyclo[5.2.102'6]-decyl cations 4 vs. oP> constants.

FIG. 2. Plot of AC(8) chemical shifts of the 8-aryl-8-

Slope of linear portion of plot.

substituents. This indicates that, as the aryl ring becomes less effective in delocalizing the positive charge at the C(2) position, the neighboring C(1)-C(6) o bond begins to interact with the empty p orbital at the cationic center-i.e., the onset of odelocalization. A recent analysis (12) of the `3C NMR chemical shift data of the 2,5-diaryl-2,5-norbornyl dications 6 shows that this approach is valid. The plot of C(1) versus C(3) in this system shows an excellent linear relationship (r = 0.998). This excellant linear fit demonstrates the similiar neighboring group deshielding effects experienced by both the C(1) and C(3) carbons. No C(1-C(6) or C(3)-C(4) or bond delocalization is occurring in these dications because the presence of two carbocationic centers renders the entire bicyclic skeleton highly electron deficient and unable to delocalize any additional charge via o, delocalization. These 2,5-diaryl-2,5-norbornyl dications are regular classical carbocations and do not show any odelocalization (12). The analysis of several other norbornyl-type systems shows

265 260

4-CF'
4-H A/ 3,5-(CF3)2

that this phenomenon is observed in all cases. The plots of the carbocationic carbon chemical shifts of the 1-aryl-l-cyclopentyl cations (10) versus the cationic chemical shifts of the 2-aryl-2bicyclo[2. 1. 1]hexyl 5 (9) and the 6-aryl-6-bicyclo[3.2. 1]octyl 7 (10) cations show linear relationships indicating the classical behavior of these aryl substituted cations. The C(1) versus C(3) [C(5) versus C(7) for cation 7] plots for these cations are also linear. The 2-aryl-2-norbornyl 3 (10, 11) and 8-aryl-8tricyclo[5.2.1.02'6]decyl 4 (10) cations both show a nonlinear plot of the cationic chemical shifts and the C(1) chemical shift of the 1-aryl-l-cyclopentyl cations. Plots of C(1) and C(3) [C(7) and C(9)] again show deviations. The data available are therefore consistent with the explanation of the onset of a delocalization causing deviations in either cationic or C(1) and C(3) chemical shift plots. Kelly and Spear (19) further argued that breaks in plots ofthe C(1) chemical shifts of the 2-aryl-2-norbornyl cations does not imply the onset of o- delocalization because they found that, when the C(1) chemical shift of the 2-aryl-2-norbornyl cation is plotted against the chemical shift of the methyl carbons of the t-cumyl cations 11 in which no or or Xr bridging is possible, an excellent straight line is obtained. They then concluded "that breaks in plots of C(1) chemical shifts of2-norbornyl derivatives cannot be used as evidence for the presence of Abridging in these cations." However, this argument is misleading. We plotted Ca shifts of several systems and observed excellent correlations. The Ca shifts of the 1-aryl-l-cyclopentyl cations (10) relate with the C(1),(3) shifts of the 2-aryl-2-adamantyl cations (r = 0.992), C(1)- of the 2-aryl-2-norbornyl cations (11) (r =
in. a.

E 255
cq

&

3,5-(CF3)2
250
Q
4

80

70 60
50

4-CF3
3-CH 4-OCH3
--

245
240
-2.0 -1.5

r
,

-`4-H
0.0
a

cls

-1.0 -0.5 rc
I

0.0

0.5

1.0

W ,;

40.

4-OCH3
-0.5 0.5
1.0

-1 .0

FIG. 1. Plot of XC(2) chemical shifts of the 2-aryl-2-norbornyl cations 3 vs. CC+ constants.

clyl cations 13 vs. a+ constants.

FIG. 3. Plot of 8C(l),C(6) chemical shifts of the 3-aryl-3-nortricy-

2002

Chemistry:

Olah et al.

Proc. Natl. Acad. Sci. USA 78 (1981)

0.994), and the methyl carbons of the t-cumyl cations (20) (r = 0.996). However, we think that these plots can be deceptive and are, in fact, not a good representation of the nature of the carbocation. It is the carbocationic carbon that the tool of increasing electron demand affects the most. The difficulty in relating C, shifts of different carbocationic systems is that the factors influencing the chemical shifts of these carbons could be quite different and dependent upon the system studied. We think that the linearity observed in the case ofthe C(l) chemical shifts ofthe 2-aryl-2-norbornyl cation versus the methyl carbon chemical shifts of the t-cumyl cations is an example of such a misleading plot and that the correlation observed is highly coincidental. A careful look at the 2-aryl-2-norbornyl data (Table 2) reveals the fallacy of this comparison. The carbocationic chemical shifts [C(2)] get progressively deshielded as stronger electron-withdrawing groups are introduced. This happens until the p-dimethylammonium substituent (8'3C = 264.6) after which a shielding is observed for the more strongly electronwithdrawing 3,5-bistrifluoromethylphenyl group (83'C = 262.8). Similiar observations can be seen for the C(3) carbon chemical shifts. Introduction ofa 3,5-bistrifluoromethylphenyl group causes a slight shielding with respect to the dimethylammonium substituent (813C 53.2-52.4). This neighboring group effect is expected for carbons a to a carbocationic center (e.g., t-cumyl or 1-aryl-l-cyclopentyl cations). However, the C(l) chemical shifts do not follow the trend ofthe cationic carbon but get progressively deshielded even with the 3,5-bistrifluoromethyl substituent. The two a-carbons [C(l) and C(3)] in the 2-aryl-2-norbornyl cations thus display different neighboring group effects. The C(3) trend of being closely related to the carbocationic chemical shift is analogous to the trend observed for the methyl carbons of the cumyl series and C. of the cyclopentyl series. It is the C(l) shifts that are abnormal and do not follow the trend of the cationic center's chemical shifts. Because the plot of'the cumyl cationic chemical shifts and the 2-aryl-2-norbornyl cationic chemical shifts is not linear, a plot of C(l) of the norbornyl system versus the methyl carbon of the t-cumyl cation is meaningless. As discussed before, a plot of two carbons within a system, such as C(l) and C(3) in the norbornyl cations, is reasonable and does reveal structural changes. But plots of a-carbons between systems should not be made unless the systems themselves behave similarly (i.e., the cationic centers are linearly related). Attempts to correlate C. and other neighboring group chemical shifts with various substituent constants have appeared recently. For example, the methyl carbon chemical shifts of the 1-aryl-l-ethyl cations 22 and 1-methyl-l-arylethyl cations 11 can be correlated to a limited degree by a+ constants (r = 0.989 and 0.990, respectively) (19). Likewise, the C(l) chemical shifts of the 2-aryl-2-norbornyl cation can be correlated quite well with c + constants (19) (r = 0.997) and the para carbon of the unsubstituted ring of a series of 4-substituted benzhydryl cations 18 shows a good correlation with c (22). Although these characteristics are dependent upon the electron demand, it is only a secondary effect and, as such, is not a true measure of the electron demand ofthe cationic center. These effects should not be dependent upon 0.C+ and indeed, they are not. One can rationalize that these diminished characteristics of the electron demand should show reasonable correlations with substituent constants which are not a true measure of the electron demand such as the a or c + constants. A further example of such correlations is in the 3-aryl-3-nortricyclyl cation 13. The onset of increased cyclopropyl conjugation can be observed with highly electron-demanding groups which consequently shields the carbocationic center. The C,3 [C(1) and C(6)] carbons, however, are significantly deshielded

due to the increased dispersal of. charge into the rigid cyclopropyl skeleton. The C,. chemical shifts should be dependent on the electron demand, although not as strongly as the cationic carbon. A plot of C. and a+ (Fig. 3) shows a good linear correlation (r = 0.994). It seems apparent that the diminished ,electron density substituent constants such as v+ or cr+ can measure, to some extent, the effect of increasing electron demand at remote sites in several carbocationic systems. However, this ability to measure a diminished electron demand in a few instances does not imply that similiar correlations can be made in different systems. Other factors play important roles in determining the effect of electron demand at a-remote site [e.g., C(1) and C(3) in the 2-aryl-2-norbornyl cations] and extreme care must be exercised in attempting such correlations.

CONCLUSIONS In conclusion the application of the tool of increasing electron demand to stable carbocations utilizing the recently developed aC+ substituent constant-13C NMR chemical shift relationship fully substantiates our previous finding from chemical shift correlations on the onset of nonclassical of delocalization in 2-aryl2-norbornyl cations 3 with electron-withdrawing substituents. Also, the observation of slopes less than unity in chemical shift correlations can reveal the nature of additional charge delocalizing mechanisms operating in the system.
EXPERIMENTAL The 2-aryl-2-adamantyl cations were generated from their alcohol precursors and studied as described (9). Support of our work' by the National Science Foundation and by the National Institutes. of Health is gratefully acknowledged. 1. Olah, G. A., Prakash, G. K. S. & Arvanaghi, M. (1980) J. Am.

4013-4016. 18. 'Brown, H. C. & Rao, C. G. (1979)J. Org. Chem. 44, 133-136. 19. Kelly, D. P. & Spear, R. J. (1978) Aust.J. Chem. 31, 1209-1221. 20. Brown, H. C., Kelly, D. P. & Periasamy, M. (1980) Proc. Natl. Acad. Sci. USA 77, 6956-6960. 21. Olah, G. A., Prakash, G. K. S. & Liang, G. (1977) J. Org. Chem.
22.

Chem. Soc. 102, 6640. 2. Jaffe', H. H. (1953) Chem. Rev. 53, 191-261. 3. Wells, P. R. (1963) Chem. Rev. 63, 171-219. 4. Stock, L. M. & Brown, H. C. (1963) Adv. Phys. Org. Chem. 1, 35-148. 5. 'Ritchie, C. D. & Sager, W. F. (1964) Prog. Phys. Org. Chem. 2, *323-400. 6. Ehrensen, S. (1964) Prog. Phys. Org. Chem. 2, 195-251. 7. Wells, P. R., Ehrensen, S. & Taft, R. W. (1968) Prog. Phys. Org. Chem. 6, 147-322. 8. Wells, P. R. (1968) Linear Free Energy Relationship (Academic, London). 9. Olah, G. A., Berrier, A. L., Arvanaghi, M. & Prakash, G. K. S. (1981) J. Am. Chem. Soc., in press. 10. Farnum, D. G., Botto, R. E., Chambers, W. T. & Lam, B. (1978) J. Am. Chem. Soc. 100, 3847-3855. 11. Olah, G. A., Prakash, G. K. S. & Liang, G. (1977)J. Am. Chem. Soc. 99, 5683-5687. 12. Olah, G. A., Prakash, G. K. S. & Rawdah, T. N. (1980) J. Am. Chem. Soc. 102, 6127-6130. 13. Brown, H. C. (commentary by P. v. R. Schleyer) (1977) The Nonclassical Ion Problem (Plenum, New York). 14. Farnum, D. G. -& Wolf, A. D. (1974) J. Am. Chem. Soc. 96, 5166-5175. 15. Richey, Jr., H. G., Nichols, J. D., Gassman, P. G., Fentiman, Jr., A. F., Winstein, S., Brookhart, M. & Lustgarten, R. K. (1970)J. Am. Chein. Soc. 92, 3783-3784. 16. Wolf, A. D. & Farnum, D. G. (1974) J. Am. Chem. Soc. 96, 5175-5181. 17. Farnum, D. G. & Botto, R. E. (1975) Tetrahedron Lett.,

42, 2666-2671.

Kelly, D. P. & Spear, R. J. (1977) Aust.j. Chem. 30, 1993-2004.