Up to six units of charge and twist-boat benzene moieties: Alkali metal reduction of phenyl-perisubstituted benzenes

Article abstract of DOI:10.1021/ja000072q

Phenyl-perisubstituted benzenes, tetraphenylbenzene (1) and hexaphenylbenzene (2), were reduced by lithium and sodium metal in THF-d₈ under high vacuum. The reduction process and the nature of the reduction products were studied by NMR. Tetraph

Full text of DOI:10.1021/ja000072q

J. Am. Chem. Soc. 2000, 122, 12637-12645
12637
Up to Six Units of Charge and Twist-Boat Benzene Moieties: Alkali
Metal Reduction of Phenyl-Perisubstituted Benzenes1
Lior Eshdat, Ari Ayalon,† Ronald Beust, Roy Shenhar, and Mordecai Rabinovitz*
Contribution from the Department of Organic Chemistry and The Lise Meitner MinerVa Center for
Computational Chemistry, The Hebrew UniVersity of Jerusalem, Jerusalem 91904, Israel
ReceiVed January 5, 2000. ReVised Manuscript ReceiVed July 17, 2000
Abstract: Phenyl-perisubstituted benzenes, tetraphenylbenzene (1) and hexaphenylbenzene (2), were reduced
by lithium and sodium metal in THF-d8 under high vacuum. The reduction process and the nature of the
reduction products were studied by NMR. Tetraphenylbenzene was reduced by both metals to yield the
corresponding dianionic salt. It was found that the addition of extra charge into the system, restricted the free
rotation of the four phenyl substituents about the σ bond connecting them to the central ring (Gq ) 7.8 (
181
0.2 kcal mol-1). The reaction of the alkali metals with 2 yielded four diamagnetic species: the first three were
assigned to the dianion, tetraanion, and the surprising hexaanion of 2. These species were calculated using
density functional theory (DFT) and were found to have central benzene rings with an unusual twist-boat
geometry. Computational and experimental evidences show that each phenyl ring and its attached carbon of
the central ring behave like a benzyl anion. We therefore view the hexaanion of 2 as a cyclohexa(benzylanion).
The fourth diamagnetic species was a product of a double-sided cyclization, which yielded the dianion of
dihydro-9,18-diphenylphenanthro[9,10-b]triphenylene (9,18-diphenyltetrabenz[a,c,h,j]anthracene dianion, 32-).
Reaction of the dianion with oxygen gave 3 in improved yields compared to literature preparations.
Introduction
attached to benzene are tetraphenylbenzene (1, n ) 4) and
hexaphenylbenzene (2, n ) 6).8 The complete reduction of 1
and that of 2 which is thoroughly studied in this contribution9
is therefore of great interest, particularly due to their key role
together with other perisubstituted benzenes in various fields
of research.10,11
Benzene, the basic subunit of π-conjugated systems, can only
be reduced to a radical anion.2 However, highly substituted
benzenes can reach the dianionic state, for example, rings that
contain four and six trimethylsilyl (TMS) substituents.3
Phenyl groups are also candidates to act as stabilizers to a
benzene dianion, by means of extending its π-system. Biphenyl
(4) is the smallest member in the family of phenyl-substituted
benzenes, which may be regarded as a benzene substituted by
one phenyl (n ) 1). Its reduced species has been studied.4,5
Other substituted benzenes of this family that were examined
are ortho, meta, and para-terphenyl5,6 (5, n ) 2), and 1,3,5-
triphenylbenzene7 (6, n ) 3). These were reduced by alkali
metals up to a radical anion or a dianion. Additional systems
which are substituted by a greater number of phenyl groups
Some general guidelines can be taken from the perisubstituted
phenyl benzene systems that have been investigated. The
substituent phenyl groups usually exhibit a pronounced charge
(6) (a) Hausser, K. H.; Mongini, L.; van Steenwinkel, R. Z. Naturforsch.,
A: Phys., Phys. Chem., Kosmophys. 1964, 19, 777-780. (b) Biehl, R.;
Dinse, K.-P.; Mo¨bius, K. Chem. Phys. Lett. 1971, 10, 605-609. (c) Plato,
M.; Biehl, R.; Mo¨bius, K.; Dinse, K. P. Z. Naturforsch. A: Phys., Phys.
Chem., Kosmophys. 1976, 31, 169-176.
(7) Jesse, R. E.; Biloen, P.; Prins, R.; van Voorst, J. D. W.; Hoijtink, G.
J. Mol. Phys. 1963, 6, 633-635.
(8) Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis; Wiley: New
York, 1968; pp 604-608.
* Corresponding author. Telephone: 972-2-6585281. Fax: 972-2-
6527547. E-mail: mordecai@vms.huji.ac.il.
(9) Reductive cyclization of 2 has been studied, see: Bock, H.; Havlas,
Z.; Gharagozgloo-Hubmann, K.; Sievert, M. Angew. Chem., Int. Ed. 1999,
38, 2240-2243.
† Current address: TAMI - IMI - Institute for R&D, POB 10140 Haifa-
Bay, Israel.
(1) This work was presented at the 15th IUPAC Conference on Physical
Organic Chemistry, July 8-13, 2000, Go¨teborg, Sweden. Program and
Abstracts p P30.
(10) For recent examples of trimerizations of 2 by organometallic
catalysis, see: (a) Yang, J.; Verkade, J. G. J. Am. Chem. Soc. 1998, 120,
6834-6835. (b) Yokota, T.; Sakurai, Y.; Sakaguchi, S.; Ishii, Y. Tetrahedron
Lett. 1997, 38, 3923-3926. (c) Chio, K. S.; Park, M. K.; Han, B. H. J.
Chem. Res., Synop. 1998, 518-519. 2 as a ligand in organometalic
complexes: (d) Ning, G. L.; Munakata, M.; Wu, L. P.; Maekawa, M.;
Kuroda-Sowa, T.; Suenaga, Y.; Sugimoto, K. Inorg. Chem. 1999, 38, 1376-
1377. (e) Mailvaganam, B.; Sayer, B. G.; McGlinchey, M. J. J. Organomet.
Chem. 1990, 395, 177-185.
(2) (a) Solodovnikov, S. P. J. Struct. Chem. 1961, 2, 272-278. (b)
Townsend, M. G.; Weissman, S. I. J. Chem. Phys. 1960, 32, 309-310. (c)
McConnell, H. M.; McLachlan, A. D. J. Chem. Phys. 1961, 34, 1-12. (d)
Jones, M. T.; Komarynsky, M.; Rataiczak, R. D. J. Phys. Chem. 1971, 75,
2769-2773. (e) Jones, M. T.; Kuechler, T. C. J. Phys. Chem. 1977, 81,
360-367. (f) Huber, W. J. Chem. Soc., Chem. Commun. 1985, 1630-1631.
(g) Dietz, F.; Rabinovitz, M.; Tadjer, A.; Tyutyulkov, N. Z. Phys. Chem.
1995, 191, 15-22.
(3) (a) Sekiguchi, A.; Ebata, K.; Kabuto, C.; Sakurai, H. J. Am. Chem.
Soc. 1991, 113, 1464-1465. (b) Sakurai, H.; Ebata, K.; Kabuto, C.;
Sekiguchi, A. J. Am. Chem. Soc. 1990, 112, 1799-1803. (c) Sekiguchi,
A.; Ebata, K.; Kabuto, C.; Sakurai, H. J. Am. Chem. Soc. 1991, 113, 7081-
7082. (d) Ebata, K.; Setaka, W.; Inoue, T.; Kabuto, C.; Kira, M.; Sakurai,
H. J. Am. Chem. Soc. 1998, 120, 1335-1336.
(4) Carrington, A.; dos Santos-Veiga, J. Mol. Phys. 1962, 5, 21-29.
(5) (a) Huber, W.; May, A.; Mu¨llen, K. Chem. Ber. 1981, 114, 1318-
1336. (b) Huber, W.; Mu¨llen, K. Acc. Chem. Res. 1986, 19, 300-306.
(11) 2 as a synthon for graphite building blocks: (a) Stable, A.; Herwig,
P.; Mu¨llen, K.; Rabe, J. P. Angew. Chem. 1995, 107, 1768-1770; Angew.
Chem., Int. Ed. Engl. 1995, 34, 1609-1611. (b) Mu¨ller, M.; Mauermann-
Du¨ll, H.; Wagner, M.; Enklemann, V.; Mu¨llen, K. Angew. Chem., Int. Ed.
Engl. 1995, 107, 1751-1754; and Angew. Chem., Int. Ed. Engl. 1995, 34,
1583-1586. (c) Mu¨ller, M.; Petersen, J.; Strohmaier, R.; Gu¨nter, C.; Karl,
N.; Mu¨llen, K. Angew. Chem., Int. Ed. Engl. 1996, 108, 947-950; and
Angew. Chem., Int. Ed. Engl. 1996, 35, 886-888. (d) Mu¨ller, M.; Ku¨bel,
C.; Mu¨llen, K. Chem. Eur. J. 1998, 4, 2099-2109. As a polymer side
chain: (e) Ku¨bel, C.; Chen, S.-L.; Mu¨llen, K. Macromolecules 1998, 31,
6014-6021.
10.1021/ja000072q CCC: $19.00 © 2000 American Chemical Society
Published on Web 12/06/2000

12638 J. Am. Chem. Soc., Vol. 122, No. 51, 2000
Eshdat et al.
Table 1. NMR Chemical Shifts of for the Li and Na Salts of 12-
compound
ortho
6.22
meta
6.61
para
5.84
ipso central
a
1
2-/2Li+ δH
-
-
7.23
(240K)
δC 121.7 127.0 109.7 139.8 108.1 137.2
6.18 6.64 5.93 7.31
δC 121.1 127.1 111.5 139.2 106.4 129.4
1
2-/2Na+ δH
-
-
(220K)
NMR was proved to be a powerful tool for the study of
structural as well as of electronic and magnetic phenomena of
diamagnetic species.17 Species with a symmetry of C3 or higher
may possess a triplet ground state for their dianions due to the
degeneracy of their LUMO π-orbitals. Such is the case for 1,3,5-
triphenylbenzene dianion, for example, which does not show
NMR spectra.18 However, due to a Jahn-Teller effect,19,20
diamagnetic dianions of highly symmetrical molecules with
singlet ground states are obtained, showing NMR spectra.21 The
high symmetry (D6) of 2 might therefore raise difficulties in
studying its charged species by NMR should a triplet state be
a dominant one. Here we report that we have achieved a
stepwise reduction of 1 and 2 by the reaction with lithium or
with sodium in THF-d8 under high vacuum and the process
follow-up by NMR. The diamagnetic products of these reactions
were analyzed by NMR techniques and were selectively
calculated using the density functional theory22 (DFT).
alternation effect.12 The ortho and para positions carry a
negative charge, while the meta and ipso positions serve as
almost neutral or slightly positive positions. An alternate
distribution of charge on phenyl groups was also observed in
heterocyclic dianions bearing phenyls.13
The barrier of rotation of the phenyl ring substituents about
the single bonds, which connect them to the central benzene
ring, was found to rise as a result of reduction, suggesting that
the motif of conjugation is increased; thus, the π-bond order
between the benzene rings is higher.5 For the same reason the
calculated torsional angle between the phenyl substituents and
the central benzene ring in the ground state of the perturbed
systems is decreased upon charging.
Reduction may also drive the molecule to a new conformation
of the central benzene ring. This behavior was found for hexakis-
(trimethylsilyl)benzene dianion by Sakurai et al.3a The benzene
ring loses the moderate chair conformation (torsional angle of
9.8°) seen in the neutral molecule, and adopts a boat conforma-
tion with localized double bonds in the dianion lithium salt as
shown by X-ray crystallography.3b This is in accord with
theoretical predictions for benzene dianion lithium complexes.14
On the other hand, the central benzene ring of 1,2,4,5-tetrakis-
(trimethylsilyl)benzene3c and the tethered hexasilyl derivated
benzene,3d which are planar, maintain their planarity in their
dianion lithium salts, thus creating an 8π electron system, which
has antiaromatic characteristics as shown by an extremely low
field 7Li NMR chemical shift (10.7 ppm). However, the effective
charge on the benzene in these systems should actually be
smaller than two electrons due to the electron-withdrawing TMS
groups.
In light of these findings, special notice should be given to
any conformational changes of the tested molecules due to their
reduction. Unlike 1,15 the solid-phase structure of 2 was
characterized by Bart et al. by X-ray crystallography.16 They
showed that the central benzene ring is planar and the six
attached phenyl groups form a propeller conformation (Φ =
67°) with a D6 symmetry. The elongation of the C-C bonds
between the central ring and each of the substituting phenyls
to merely a single bond (1.47-1.53 Å) is evidence for only
partial conjugation.
Results and Discussion
Reduction of Tetraphenylbenzene (1). Reaction of 1 with
sodium or lithium yields a thermochromic diamagnetic species,
blue at room temperatures, which within a few hours turns red
1
at -78 °C. The centers of gravity23 of the H NMR and 13C
NMR of the new species are shifted to higher fields with an
overall change in 13C chemical shift (ΣδC) of 283 ppm, in line
with a formation of a dianion (Table 1). The chemical shift of
the ortho protons broadens and decoalesces (180.5 K; 5.94 ppm)
into two broad signals at lower temperatures (165 K; 4.90, 6.93
ppm). In contrast, the spectrum of the neutral molecule does
1
not show any spectral temperature dependence (13C and H
NMR) even at 165 K. This behavior is attributed to an enhanced
barrier of rotation of the phenyls due to reduction, that is, 7.8
( 0.2 kcal mol-1 at the coalescence temperature compared to
an upper limit of 5.0 ( 0.2 kcal mol-1 for the neutral
(17) For recent general references, cf.: (a) Minkin, V. I.; Glukhovtsev,
M. N.; Simkin, B. Ya. Aromaticity and Antiaromaticity; Wiley: New York,
1994 . (b) Baumgarten, M.; Mu¨llen, K. Top. Curr. Chem. 1994, 169, 3-103.
(c) Schleyer, P. v. R.; Jiao, H. J. Pure Appl. Chem. 1996, 68, 209-218. (d)
Rabinovitz, M.; Benshafrut, R.; Shabtai, E.; Scott, L. T. Eur. J. Org. Chem.
2000, 1091-1106.
(18) For more examples of anions with high symmetry, cf.: (a) Hoijtink,
G. J. Mol. Phys. 1959, 2, 85-95. (b) Jesse, R. E.; Biloen, P.; Prins, R.; van
Voorst, J. D. W.; Hoijtink, G. J. Mol. Phys. 1963, 6, 633-635. (c) van
Willgen, H.; van Broekhoven, J. A. M.; de Boer, E. Mol. Phys. 1967, 12,
533-548. (d) van Broekhoven, J. A. M.; van Willgen, H.; de Boer, E. Mol.
Phys. 1968, 15, 101-103. (e) Gherghel, L.; Brand, J. D.; Baumgarten, M.;
Mu¨llen, K. J. Am. Chem. Soc. 1999, 121, 8104-8105.
(19) Jahn, H. A.; Teller, E. Proc. R. Soc. 1937, A161, 220-235.
(20) (a) Wert, J. E.; Bolton, J. R. ESR Elementary Theory and Practical
Applications; McGraw-Hill: New York, 1972; pp 232-246. (b) Breslow,
R. Pure Appl. Chem. 1982, 54, 927-938.
(21) (a) Sommerdijk, J. L.; de Boer, E.; Pijpers, F. W.; van Willigen, H.
Z. Phys. Chem. (Wiesbaden) 1969, 63, 183-189. (b) Baumgarten, M.;
Gherghel, L.; Wagner, M.; Weitz, A.; Rabinovitz, M.; Cheng, P.-C.; Scott,
L. T. J. Am. Chem. Soc. 1995, 117, 6254-6257.
(12) (a) Klein, J. Tetrahedron 1983, 39, 2733-2759. (b) Cohen, Y.;
Klein, J.; Rabinovitz, M. J. Am. Chem. Soc. 1988, 110, 4634-4640.
(13) (a) Cohen, Y.; Klein, J.; Rabinovitz, M. J. Chem. Soc., Chem.
Commun. 1987, 1538-1540. (b) Cohen, Y.; Klein, J.; Rabinovitz, M. J.
Chem. Soc., Perkin Trans. 2 1988, 31-38.
(14) (a) Podlogar, B. L.; Glauser, W. A.; Rodriguez, W. R.; Raber, D.
J. J. Org. Chem. 1988, 53, 2127-2129. (b) Sygula, A.; Rabideau, P. W. J.
Am. Chem. Soc. 1991, 113, 7797-7799.
(15) (a) Harada, K.; Hart, H.; Du, C.-J. F. J. Org. Chem. 1985, 50, 5524-
5528. (b) Saednya, A.; Hart, H. Synthesis 1996, 1455-1458.
(16) Bart, J. C. J. Acta Crystallogr. 1968, B24, 1277-1287.
(22) (a) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and
Molecules; Oxford University Press: Oxford, 1989. (b) Ziegler, T. Chem.
ReV. 1991, 91, 651-667. (c) Laird, B. B.; Ross, R. B.; Ziegler, T., Eds.
Chemical Applications of Density Functional Theory; ACS Symposium
Series 629; American Chemical Society: Washington, DC, 1996. (d) Kohn,
W.; Becke, A. D.; Parr, R. G. J. Phys. Chem. 1996, 100, 12974-12980.
(23) The center of gravity of the spectrum is defined as the average of
the chemical shifts, normalized by their relative integration.

Twist-Boat Benzene Moieties
J. Am. Chem. Soc., Vol. 122, No. 51, 2000 12639
Table 2. Experimental and Calculated (GIAO B3LYP/6-31G*//B3LYP/6-31G*) NMR Chemical Shifts of for the Li and Na Salts of 22-, 24-
and 26-
,
compound
2-/2Li+ (200 K)
ortho
meta
6.55
127.2
6.55
127.4
5.89
111.8
7.17
para
ipso
central
2
δH
δC
δH
δC
δH
δC
δH
6.42
6.18
116.4
6.16
115.8
5.21
97.8
6.49
-
-
128.4
6.34
128.3
6.39
114.7
7.67
144.9
117.1
2
2-/2Na+ (220 K)
-
143.8
-
133.8
-
-
117.5
-
119.5
-
22- - calculateda
2-/Li(dimethyl ether)2
+
2
(calculated)a
δC
δH
δC
δH
δC
δH
117.4
5.56
121.7
5.35
-
116.2
6.25
127.3
6.30
-
106.6
5.37
103.4
5.13
-
134.9
-
140.4
-
-
-
112.5
-
99.5
-
-
-
2
2
4-/4Li+ (200 K)
4-/4Na+
24-
(calculated)
5.02
4.74
2.83
δC
δH
112.7
3.78
4.64, 4.79
-
3.47
4.55, 4.81
120.6
117.5, 107.5
4.74
109.0
6.28
6.35, 6.00
-
6.19
6.36, 5.96
125.9
130.1, 127.7
4.68
77.5
4.49
4.55
-
4.27
4.35
87.9
88.4
2.86
106.6
-
-
-
-
-
124.6
123.5
-
147.7
-
-
-
-
-
96.2
93.4
-
2
6-/6Li+ (180 K)
6-/6Na+ (180 K)
ABB′CC′
ABCDE
δC
δH
2
ABB′CC′
ABCDE
ABB′CC′
ABCDE
ABB′CC′
δC
δH
26-
(calculated)
ABCDE
ABB′CC′
ABCDE
5.06, 5.25
117.3
106.4, 114.3
4.95, 4.60
109.4
111.6, 106.0
2.81
78.1
77.2
-
-
δC
117.5
101.2
169.0
137.1
a Averaged values are presented to facilitate the comparison with the experimental data. Optimized TMS isotropy (D2d: 1H: 31.92; 13C: 183.73).
due to the formation of a radical anion. Further contact with
the metal changes the color of the solution to brown, and a
new 1H NMR spectrum (Table 2) evolves, with a typical phenyl
pattern (ABB′CC′), which is shifted to a higher field (6.20-
6.59 ppm) compared to the H NMR of the neutral 2. The 13C
1
Figure 1. Experimental (13C NMR) charge distribution in 12-
.
NMR spectrum is also shifted to a higher field with ΣδC of
240 ppm, a typical value for doubly charged aromatic polycyclic
systems. When this species is quenched with molecular oxygen,
the parent 2 is recovered, while reaction with D2O yields
dideuteriohexaphenylbenzene (m/z ) 538). We therefore assign
this species to the dianion (22-).
compound.24 Such behavior is absent for the meta protons,
probably because the difference between the magnetic environ-
ments of the two sites is not too large.25 Reaction of the reduced
species with D2O yielded the dideutero derivative (m/z ) 386),
while quenching with oxygen regenerated the starting material
1. Due to these findings, we assign this species to the dianion
of 1 (12-).
Charge distribution in 12-. The charge distribution was
calculated from the change in the 13C NMR chemical shifts upon
reduction (see experimental).26 The two charge units are evenly
distributed between the four phenyls and the four carbons of
the central ring to which they are attached (Figure 1). The
substituent phenyl groups exhibit a pronounced charge alterna-
tion effect. The two carbons of the central benzene, which do
not carry phenyls, serve as noncharged nodes between the two
pairs of carbons which are substituted by phenyls, thus complet-
ing an overall charge alternation pattern.
When the brown dianion solution is kept in contact with the
lithium wire, a new 1H NMR spectrum appears with no apparent
change in the color of the solution. The new 13C and 1H NMR
spectra show the same pattern as the former (i.e., ABB′CC′);
however, all lines are shifted upfield (1H NMR center of gravity
) 5.79 ppm, ΣδC ) 510 ppm). The 2-fold shielding effect of
the NMR spectra and the formation of tetradeutero2 upon
quenching with D2O (as a major product; m/z ) 542), as well
as the recovery of 2 upon reaction with O2, all point to the
assignment of this species as the tetraanion of 2 (24-).
When 2 in THF-d8 is reduced by sodium (Figure 2), the first
stages of reduction are very similar to that of lithium reduction.
The neutral spectrum broadens, the color changes to green and
afterward to brown, and the spectrum of the 22- appears with
only minor differences (Figure 2b). However, the next step
differs somewhat. After a continuous and prolonged contact of
the solution with the metal, a third set of spectral lines appears
beside those of 22- and of 24- (Figure 2c). As the third set
rises, the pattern of 22- declines while that of 24- remains as a
steady-state intermediate between the 22- and the third species.
When the reaction with the metal is carried out at temperatures
higher than room temperature or at -78 °C, then the dianion
and the traces of the tetraanion disappear, and the spectrum
consists solely of the third set of lines (Figure 2d). In contrast
Reduction of Hexaphenylbenzene (2). Reduction of the
colorless solution of 2 in THF-d8 by lithium metal first affords
1
a green solution. The H NMR spectrum broadensspossibly
(24) Sandstro¨m, J. Dynamic NMR Spectroscopy; Academic Press: New
York, 1982; pp 93-97.
(25) A similar dynamic behavior was observed for the dianion of ortho-
terphenyl (ref 5).
(26) (a) Freankel, G.; Carter, R. E.; Mclachlan, A.; Richards, J. H. J.
Am. Chem. Soc. 1960, 82, 5846-5850. (b) Farnum, D. G. In AdVances in
Physical Organic Chemistry; Gold, V.; Bethell, D., Eds.; Acadaemic
Press: London, 1975; Vol. 11, pp 123-175. (c) Eliasson, B.; Edlund, U.;
Mu¨llen, K. J. Chem. Soc., Perkin Trans. 2 1986, 937-940. (d) Mu¨llen, K.
Chem. ReV. 1984, 84, 603-646.

12640 J. Am. Chem. Soc., Vol. 122, No. 51, 2000
Eshdat et al.
1
Figure 2. Na reduction of 2 followed up by H NMR at 190 K. (a) 2; (b) 22-; (c) 22-, 24-, and 26- in equilibrium; (d) 26-
.
to the former charged species, the 13C and 1H NMR spectra of
this new species exhibit a lower symmetry, which includes two
types of phenyls with ABCDE and regular ABB′CC′ NMR
patterns in the ratio of 2:1, respectively. The 13C NMR possesses
12 different peaks including four quaternary carbons. This
observation suggests that the central benzene ring also loses its
total (D6) symmetry and one can identify two different types
of the central ring carbons in the ratio of 2:1 as well.
tions lead us to suggest that 22- is in equilibrium with the higher
reduced 24- (as a steady-state intermediate) and 26-. The
coexistence of three diamagnetic species with only moderate
broadening of their lines (up to approximately 10 Hz) is possible
if the intermediary paramagnetic radical stages are of very low
concentrations. The reduction process is therefore:
2 + 6Na h 22-/2Na+ + 4Na h
24-/4Na+ + 2Na h 26-/6Na+
The proton chemical shifts of the ortho and the para positions
are shifted to a very high field (3.47-4.81 ppm), while the meta
protons are less affected (5.96-6.36 ppm). The total center of
gravity moves to 5.04 ppm, which is approximately 0.7 ppm
upfield compared to 24-. This is in the order of the difference
between the centers of gravity of 24- and 22-. This suggests
that after reduction to a dianion, which is followed by a
tetraanion, the reduction finally results in a third species, which
Unlike reduction of 2 with sodium, 26- lines can hardly be seen
upon reduction with lithium only if the reduction is held above
room temperatures or after weeks of charging at low temper-
atures. There is a 0.5 ppm difference in the chemical shifts of
one of the ABCDE ortho protons of 26-/6Li+ as compared to
that of 26-/6Na+ possibly due to different ion solvation
equilibria.
is the highly charged hexaanion of 2 that is, 26- 27 The 13C NMR
.
spectrum offers extra support to a hexaanion assignment, with
ΣδC ) 819 ppm, that is, six charges that yield KC ) 136.5 ppm/
e26 which is in the same order as those of 22- and of 24-. This
value shows a linear trend of higher KC values as more electrons
are added to the system. The possibility that the third species
is a product of a chemical reaction that involves breaking or
formation of new bonds is ruled out by the following ob-
servations: (a) the parent 2 is recovered after quench of with
O2; (b) a ROESY exchange cross-peak between the two types
of para protons,28 which indicates that the ABCDE is indeed a
phenyl group, and not a fixed benzo substituent, and (c) there
is no signal in the sp3 region in the 13C NMR spectrum indi-
cating that it is not a protonation product or a cyclization
intermediate.29
7
The Li NMR chemical shifts of the Li+ counterions at 200
K are -1.08, -1.45, and -2.54 ppm for the corresponding 22-
,
7
2
4-, and 26- respectively. The appearance of the Li bands in
this region indicates that the cations are most likely solvent
separated, despite the likelihood that highly charged systems
such as the tetra and the hexaanions would attract the counter-
cations to form contact ion pairs (CIP). In light of these findings
we calculated the anions of 2 without considering countercations
or solvent molecules. The calculations were done by using the
DFT approach and employing Becke’s three-parameter exchange
functional30 (B3) along with the nonlocal correlation functionals
of Lee, Yang, and Parr31 (LYP) and the 6-31G* basis set.32
The most stable singlet states of the “bare” anions refer to
minimum structures with a central benzene ring in a twist-boat
conformation, which have D2 (22- and 24-) or C2 symmetry
(26-; the deviation from D2 symmetry is rather small). In
contrast, the optimized structure of the uncharged 2 is character-
ized by a propeller-style D6 arrangement as has been found by
2
6- is stable for days at -78 °C. However, when the solution
containing 26- is not brought in contact with the metal, then
the process reverts and the spectrum of 22- reappears until 26-
totally vanishes while metallic-like dust appears. These observa-
(27) It should be noted that reaction with MeI or with D2O gave a mixture
of unresolved products.
(30) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
(31) (a) Lee, C.; Yang, W.; Parr, R. G. Phys. ReV. B 1988, 37, 785-
789. (b) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett.
1989, 157, 200-206.
(32) (a) Hehre, W. J.; Ditchfield, R.; Pople J. A. J. Chem. Phys. 1972,
56, 2257-2261. (b) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973,
28, 213-222.
(28) Appearance or lack of ROESY exchange cross-peaks between the
ortho and meta protons does not indicate the existence of an exchange
process because these protons also have NOE correlations.
(29) Formation of benzo[ghi]perylene dianion from [5]-helicene di-
anion: Ayalon, A.; Rabinovitz, M. Tetrahedron Lett. 1992, 33, 2395-2398.

Twist-Boat Benzene Moieties
J. Am. Chem. Soc., Vol. 122, No. 51, 2000 12641
Figure 4. Addition of charge on 26- compared with 24-
.
served as a model for the chemical shift of a hypothetical
hexaphenylbenzene with a nonaromatic central benzene ring.
In the dianion, 1.3 electrons of the charge are located on the
central ring, while the remaining 0.7 electron is spread over
the six phenyls. This is opposed to standard expectation of
separation of the charge to the remote corners of the molecule
instead of concentrating the charge in the center of the molecule.
However, in the former charge distribution each phenyl loses
much of its aromaticity. In contrast, if only the central benzene
ring “sacrifices” its aromaticity, while the rest hardly do so, it
should behave like a system with three double bonds carrying
phenyl groups, (such as the vinyl carbons of styrene) which
are known to localize extra charge.17
Figure 3. Charge distribution in the anions of 2. (a) Experimental
(13C NMR); (b) calculated (NBO (B3LYP/6-31G*)). Due to the D2
symmetry, there are several values with small differences for a specific
position, but the calculated values of 22- and 24- were averaged to
simplify the comparison with the experimental elucidation (which shows
an average for these anions).
The phenyl substituents exhibit a charge alternation pattern,
similar to that of the substituting phenyls in 12-. The charge
Table 3. Coupling Constants between Carbons of the Central Ring
and the ipso Carbons of the Phenyl Substituents in the Anions of 2
1
alternation is in line with the observation of broader H NMR
neutral
22-
58
32 (sp2)
24-
63
36 (sp2)
26-
lines of the para and ortho protons as compared to that of the
meta protons.
1JCC (Hz)
% s (hybridization)
36
-
-
26 (sp3)
The central benzene component bears a net charge of two
electrons upon reduction of the 2 parent system to a tetraanion;
therefore, it is an unprecedented example in which two units of
charge reside on a benzene ring in a highly charged system. At
the same time, the phenyl substituents maintain the charge
alternation pattern, while the six para carbons hold one unit of
charge and the twelve ortho carbons another unit of charge.
According to the 13C NMR analysis, the introduction of two
more electrons to the system, thus creating a hexaanion, adds
the extra charge (Figure 4) exclusively to the peripheral phenyl
rings, while a total of two charges remains on the carbons of
the central ring. The charge alternation structure partly collapses,
as the ipso position receives a significant amount of the
additional charge, while the meta carbons remain almost neutral.
The DFT calculated charge distribution (derived from Natural
Bond Order (NBO)35 analysis using B3LYP/6-31G*)36 of the
three anions of 2 in their twist boat geometry is presented in
Figure 3b.37 These calculations suggest that most of the net
charge resides on the attached phenyl groups and is concentrated
mainly on the para and meta positions without exhibiting a
X-ray crystallography:16 The carbon-carbon bond lengths
within the central six-membered ring and between the central
ring and each substituting phenyl amount to 1.41 and 1.50 Å
respectively, and the dihedral angle between the substituting
phenyls and the plane of the central ring is 65°.
Charge Distribution in the Anions of 2. We determined
the charge distribution according to the differences between the
13C NMR spectra of the anions and of the neutral compound
(Figure 3a; see Experimental Section).26 To establish the 13C
NMR assignment of the central ring carbons we synthesized a
13C-enriched 2 in the 1,4 positions (2-13C2) by a Diels-Alder
reaction between a 13C-labeled tetraphenylcyclopentadienone
and diphenyl acetylene. The labeling enabled the evaluation of
the degree of conjugation between the phenyls by calculating
the s character from the carbon-carbon coupling (1JCC) between
the central ring carbons and the ipso carbons of the phenyls.33
The results (Table 3) show an increase of the s character as the
system carries more charge, thus indicating charge distribution
via conjugation.
(35) (a) Foster, J. P.; Weinhold, F. J. Am. Chem. Soc. 1980, 102, 7211-
7218. (b) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1983, 78, 4066-4073.
(c) Reed, A. E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736-1740.
(36) A reviewer suggested the use of diffuse functions in these calcula-
tions, which are well-known to better mirror the energetic properties of
anions by reducing the mutual repulsion between the extra charge and the
other electrons (Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer,
P. v. R. J. Comput. Chem. 1983, 4, 294-301). Due to restrictions of
computational sources we could not apply the 6-31+G* basis set (that
includes diffuse functions) to all the calculated anions except for 22-, in
which the picture did not change dramatically. We believe, that because
the charge in PAH anions is efficiently distributed over the entire π-system
rather than localized on specific atoms, no special means need to be taken
to reduce the overestimated mutual electron repulsion in this type of anions.
(37) We are aware of the arbitrariness incorporated in the estimation of
the partial charges from calculation (since charge distribution is not a
quantum mechanical observable). However, we believe that this method of
estimation is especially meaningful for PAHs since they contain only carbon
in their π-framework, therefore the approximation incorporated in the
decision how to split the charge between two neighboring atoms is not
harsh due to mutual compensation of the errors.
Elucidation of the charge distribution from the differences
in the 13C NMR spectra is based on the assumption that extra
shielding is proportional to the additional charge carried by a
specific carbon.26 The high field shift of the carbons in all the
three species may also result from the loss of the aromatic nature
of the central benzene ring. The calculations mentioned above
suggest that the central ring adopts a twist-boat conformation.
It follows that the central six-membered ring is no longer a
benzene ring as the π orbitals can merely overlap in such a
conformation. For this reason instead of using 2 as the neutral
reference, the chemical shifts of the hindered phenyls (and the
carbon they are attached to) of tetraphenylcyclopentadiene (7)34
(33) Hansen, P. E. Prog. Nucl. Magn. Reson. Spectrosc. 1981, 14, pp
189 and references therein.
(34) Schumann, H.; Janiak, C.; Zuckerman, J. J. Chem. Ber. 1988, 121,
207-218.

12642 J. Am. Chem. Soc., Vol. 122, No. 51, 2000
Eshdat et al.
Table 4. Calculated (B3LYP/6-31G*) Bond Lengths and Dihedral
Angles between the Peripheral Phenyls and the Central Benzene
Ring of the Two Speciesa
charge alternation pattern. This stands in some distortion to the
charge distribution estimated from the 13C NMR shifts. The
calculated NMR chemical shifts (calculated by the gauge-
including atomic orbitals (GIAO)38 method on the B3LYP/6-
31G* level), which are given in Table 2, in general reflect the
same distortion. Despite these differences, there is a reasonable
agreement with the experimental data as shown by correlations
between the two sets of data ranging from 0.50 to 0.80. Better
correlations are obtained when 7 is used as the neutral reference
for the experimental elucidation rather than 2, which lends
strength to the finding of loss of aromaticity of the central
benzene ring and to the cyclohexa(benzylanion) model (see
below). The best correlation is found when the contact ion pair
system (CIP) of 22-/Li+ is calculated in which one Li+ cation
is coordinated to two dimethyl ether molecules (as a model for
THF) and to the central benzene ring of the dianion, which
compound
d Ccentral-Cipso (Å)
average dihedral angle (deg)
2
1.50 (1.47-1.53)
1.49, 1.45
1.45, 1.43
64.97 (∼67)
42.22, 10.54
24.11, 8.70
18.58, 7.10
22-
24-
26-
1.42, 1.41
a Data from X-ray crystallography16 are presented in parentheses.
The paired values are of the two and four equivalent phenyls of the
twist boat structure, respectively. The dihedral angle of the latter was
calculated by the average of all possible dihedral angles of the carbons
that are adjacent to the central and ipso carbon atoms.
latter values are typical values for single carbon-carbon bonds.
The Ccentral-Cipso bonds have shorter bond lengths and smaller
dihedral angles, compared to the neutral parent 2 (Table 4). This
is in accordance with the Ccentral-Cipso bond lengths that were
calculated from the Jcc values of the anions of 2-13C2, and in
line with what was found for other phenyl-substituted systems.4,5
7
adopts boat structure. Still, relying on the Li NMR chemical
shifts, the solvent separated ion system forming the twist-boat
conformation is most probably the dominant structure in
solution. We believe that the calculations are somewhat limited
in predicting charge distribution in a condensed phase. Perhaps
taking the solvent, the countercations and all solvation states
into account would give better correlation to experiment. Such
a complex calculation however, is beyond the scope of this
work. Since calculations are performed on single points in the
conformational hyper-surface, whereas NMR data gives an
average picture, it seems that a comparison between the two
methods is somewhat problematic. Therefore, we believe that
NMR, as far as charge distribution is concerned, gives a more
realistic picture that is in line with studies12,13 on related
compounds. The calculations contribute to our understanding
of the preferred conformations especially when the NMR shows
only an average picture as in the cases of 22- and 24-. We feel
that both approaches contribute to our understanding in a
complementary way.
The experimental charge distribution of each phenyl ring39
and the attached central ring carbon resembles very much a
benzyl anion.40 The system may be viewed as a cyclohexa-
(benzylanion), that is, a group of six benzyl anions linked to
each other in the benzyl positions. Alternatively, it may also
be envisioned as two units of cis-stilbene separated by two
benzyl anions. cis-Stilbene and its derivatives are well-known
to isomerize to trans-stilbene as a result of reduction to dianion
even under steric constraints;41 therefore, the hexaphenylbenzene
anions afford a special opportunity to have a glimpse at a fixed
form of reduced cis-stilbene.
Cyclization of 22- and Formation of Dihydro-9,18-diphenyl-
phenanthro[9,10-b]triphenylene dianion (32-). After few
weeks of storage at below -15 °C of both the lithium and
sodium salts, a new species appeared in coexistence with the
anions of 2, having a typical phenyl pattern (ABB′CC′) and an
ABCD pattern in the ratio of 1:2 (Table 5). We were inclined
to conclude that this is a product of a dehydrogenation
cyclization reaction, which is well-known for other dianionic
systems.29,42-44 Two pairs of the periphery phenyls undergo
dehydrogenation cyclization to phenantrecene units and two
phenyls remain nonreacted. The two remaining phenyls must
be para to each other, otherwise the phenantrecene units would
have lost symmetry and would have exhibited two different
ABCD patterns. This NMR pattern is in line with the formation
of a reduced species of 3. Treatment with oxygen yielded 3.45
1
The H NMR spectrum is shifted upfield to that of what was
reported for 3,45 implying that it belongs to an anion. The 13C
NMR is shifted upfield typically to a dianion (ΣδC ) 270 ppm).
The conclusion that the reduction state is of a dianion, was
strengthened after Bock et al. reported the crystallization from
dimethoxyethane (DME) of [32-/Li+(DME)2]-Li+ as the reac-
tion product of 2 with lithium powder.9
The mechanism’s pathway should go through the tetrahydro
intermediate similarly to what was suggested for the dehydro-
genation cyclization of ortho terphenyl dianion and of 2,3-
diphenylquinoxaline dianion42,43 and found for [5]-helicene
dianion.29 Such a mechanism is also suggested and supported
by semiempirical calculations performed by Bock et al.9 Their
suggested mechanism starts from the boat conformation of
[22-Li+(DME)2]-, which is reported as a minimum structure.
The lithium atom which is considered as forming a contact ion
pair is coordinated to two carbon atoms at the tips of the central
ring as well as to either oxygen atom of two solvent molecules
(DME). The second lithium cation necessary for overall
The structural parameters from the DFT calculations strongly
support the cyclohexa(benzylanion) model. The bond lengths
within the central six-membered ring increase as the charging
of the system proceeds. Starting with a bond length of 1.41 Å
in the neutral system, they amount to 1.42 (for the four bonds
of the same type in the D2 symmetry) and 1.52 Å (the remaining
two bonds of the other type) in the dianion, 1.46 and 1.53 Å in
the tetraanion and reach 1.51 and 1.54 Å in the hexaanion. The
(38) Wolinski, K.; Hilton, J. F.; Pulay, P. J. Am. Chem. Soc. 1990, 112,
8251-8260.
(42) Formation of triphenylene dianion from ortho terphenyl dianion:
Tamarkin, D. Ph.D. Dissertation, The Hebrew University of Jerusalem,
Jerusalem (1987).
(43) Formation of dibenzo[a,c]phenazine dianion from 2,3-diphenyl-
quinoxaline dianion: (a) Smith, J. G.; Levi, E. M. J. Organomet. Chem.
1972, 36, 215-226. (b) Eisch, J. J. Prepr. - J. Am. Chem. Soc. - Pet.
Chem. 1986, 31, 798-802. (c) Cohen, Y.; Meyer, A. Y.; Rabinovitz, M. J.
Am. Chem. Soc. 1986, 108, 7039-7044.
(44) (a) Koch, K. H.; Mu¨llen, K. Chem. Ber. 1991, 124, 2091-2100.
(b) Koch, K. H.; Fahnenstich, U.; Baumgarten, M.; Mu¨llen, K. Synth. Met.
1991, 42, 1619-1622.
(45) Pascal, R. A., Jr.; McMillan, W. D.; Van Engen, D.; Eason, R. G.
J. Am. Chem. Soc. 1987, 109, 4660-4665.
(39) To normalize chemical shift difference that arises from conforma-
tional differences we calculated the charge density out of the aVerage
chemical shift of the two ortho positions.
(40) (a) Russell, G. A. J. Am. Chem. Soc. 1959, 81, 2017-2022. (b)
Bockrath, B.; Dorfman, L M. J. Am. Chem. Soc. 1974, 96, 5708-5715.
(41) (a) Wang, H. C.; Levin, G.; Szwarc, M. J. Am. Chem. Soc. 1977,
99, 2642-2647. (b) Nozaki, K.; Naito, A.; Ho, T.-I.; Hatano, H.; Okazaki,
S. Chem. Lett. 1989, 511-514. (c)Yokoyama, Y.; Koizumi, T.; Kikuchi,
O. Chem. Lett. 1991, 2205-2208. (d) Gano, J. E.; Jacob, E. J.; Sekher, P.;
Subramaniam, G.; Eriksson, L. A.; Lenoir, D. J. Org. Chem. 1996, 61,
6739-6743.

Twist-Boat Benzene Moieties
J. Am. Chem. Soc., Vol. 122, No. 51, 2000 12643
Table 5. NMR Chemical Shifts of for the Li and Na Salts of 32-
compound
1
2
3
4
4a
8a
8b
9
ortho
meta
para
ipso
3
δH
δC
δH
δC
δH
δC
7.19
6.90
7.34
8.40
-
133.0
-
129.6
-
-
131.6
-
133.7
-
-
131.3
-
136.4
-
-
7.39
134.3
6.28
114.9
6.09
7.34
130.4
6.39
127.2
6.30
7.38
128.5
5.56
106.1
5.40
-
144.5
-
140.7
-
(298 K)
3
130.8
8.16
130.2
8.10
130.3
125.9
7.21
124.0
7.26
124.5
127.2
7.11
121.2
7.16
121.4
124.2
8.45
122.7
8.52
122.7
135.0
-
86.5
-
2-/2Li+
(270 K)
2-/2Na+
(270 K)
3
129.3
133.4
136.6
87.4
111.9
128.4
104.3
139.6
Following the process of the reaction in a NMR tube showed
that heating the brown anionic mixture in contact with the metal
pushes the reaction toward the formation of the 26- and this
inhibits the dehydrogenation reaction. The concentration of 32-
raises only when the solution is kept without the metal and is
accompanied by the appearance of small gray particles. This
supports the suggested mechanism in which 32- originates from
22- (here regenerated from 26-).9 Therefore, we synthesized 3
from 2 by treatment of 2 in THF solution with lithium wire
and immediately after reaching a brown color, the solution was
detached from the metal and was warmed at 65 °C for 24 h.
The solution was then quenched with O2 and the product was
purified by solid-phase chromatography from the remaining 2,
giving 3 in 27% yield (see Experimental Section).
Figure 5. Experimental (13C NMR) charge distribution in 32-
.
neutrality is considered as being solvent-separated and was
therefore omitted.
In our calculations, we confirm that the (imperfect) boat
conformation of [22-Li+(CH3-O-CH3)2]- refers in fact to a
minimum structure. However, according to the experimental 7Li
NMR findings, there is only one type of lithium atom exhibiting
a resonance in the solvent separated ion pair (SSIP) region of
-1.08 ppm.46 In light of this circumstance, one could propose
an alternative mechanism for the formation of 32-, starting from
the twist-boat conformation of 22-. Otherwise, the SSIP system
with the 22- having a twist boat conformation may be the
dominant species in solution while the species which yields the
cyclization product is the less common CIP 22-/Li+ with the
boat conformation. We also find it intriguing to find out whether
the dehydrogenation occurs simultaneously in both sides or
consecutively, and whether the sp3 hybridized hydrogens are
syn or anti to each other.
Conclusions
Reduction of 1 and 2 was achieved by their reaction with
lithium or with sodium in THF-d8 under high vacuum and was
monitored by NMR. While 1 gave only one charged product,
tetraphenylbenzene dianion (12-), 2 offered three charged
diamagnetic species of 2 in addition to a charged cyclization
product, namely the dianion of dihydro-9,18-diphenylphenan-
thro[9,10-b]triphenylene (32-). In addition to the experimental
determination of the charge distribution of 32- by NMR, we
described a stepwise reduction of 2 showing that 22- is not only
a synthon of 32- but is also the precursor of highly charged
loaded π-systemssthe tetraanion and hexaanion of 2. Utilizing
the metal reduction of 2 as described here offers an accessible
method to prepare 3.
Charge Distribution in 32-. The elucidation of the charge
distribution from the 13C NMR47 shows that the phenanthrecene
units, which are fused to the central benzene ring, carry only a
very small amount of charge while most of it (0.35 e-) is
localized on the 9,10-benzylic positions (Figure 5). The rest of
the charge is held by the phenyls in a charge alternation fashion,
where the charge is mainly located on the ortho and para
positions. These results are in excellent agreement to the
calculated charge distribution except for the lower calculated
charge density at the ortho position.9 The agreement between
experiment and calculations shows that the use of the 13C
chemical shifts of the neutral axially twisted 3 for extracting
the charge distribution is legitimate despite the conformational
differences of 32-, which was found to have a boat conformation
held by a Li+ “glue” in the solid phase.9 The same conformation
is also likely to exist in solution due to the high charge density
at the benzylic position, which is found by NMR.
Outlook
The remarkable ability of fullerenes as well as of polycyclic
aromatic hydrocarbons (PAHs) to reversibly store electrons has
stimulated interest in their use as new charge storage materials.
The cyclohexa(benzylanion) revealed in this work carries six
units of charge over seven carbon rings and has a better
capability for electron storage, that is, six electrons on 42
carbons a 1:7 ratio as opposed to C60 which can carry six
electrons48 with a 1:10 ratio. 2 joins other PAH systems, which
we have recently shown to be highly charged with excellent
charge-to-carbon ratios.49,50 Therefore, in addition to their
theoretical importance,17 the highly charged PAHs may
thereby be even more attractive than fullerenes as molecular
batteries.
Isolation of 3. The synthesis of 3 by Pascal et al.45 was carried
out by the heating phenyclone and 9-bromophenanthrene at 340
°C in a yield of 4%, whereas in our NMR investigations we
obtained a pure solution of 32- in THF-d8. We therefore checked
whether the alkali reduction of 2 would give higher yields.
(48) (a) Xie, Q.; Pe´rez-Cordero, E.; Echegoyen, L. J. Am. Chem. Soc.
1992, 114, 3978-3980. (b) Haddon, R. C. Acc. Chem. Res. 1992, 25, 127-
133. (c) Bausch, J. W.; Prakash, G. K. S.; Olah, G. A.; Tse, D. S.; Lorents,
D. C.; Bae, Y. K.; Malhotra, R. J. Am. Chem. Soc. 1991, 113, 3205-3206.
(d) Shabtai, E.; Weitz, A.; Haddon, R. C.; Hoffman, R. E.; Rabinovitz, M.;
Khong, A.; Cross, R. J.; Saunders, M.; Cheng, P.-C.; Scott, L. T. J. Am.
Chem. Soc. 1998, 120, 6389-6393.
(49) Weitz, A.; Shabtai, E.; Rabinovitz, M.; Bratcher, M. S.; McComas,
C. C.; Best, M. D.; Scott, L. T. Chem. Eur. J. 1998, 4, 234-239.
(50) Benshafrut, R.; Rabinovitz, M.; Dee-Noor-Barzilay, Z.; de Meijere,
A. J. Phys. Org. Chem. 1999, 12, 333-339.
(46) (a) Cox, R. H.; Terry, H. W., Jr.; Harrison, L. W. J. Am. Chem.
Soc. 1971, 93, 3297-3298. (b) Cox, R. H.; Terry, H. W., Jr. J. Magn. Res.
1974, 14, 317-322. (c) Gu¨nther, H.; Moskau, D.; Bast, P.; Schmalz, D.
Angew. Chem. 1987, 99, 1242-1250. Angew. Chem., Int. Ed. Engl. 1987,
25, 1212-1220.
(47) The 13C NMR spectrum of 3 was not available in the literature. We
fully assigned the neutral 3 to calculate the charge distribution of the anion.
13C enriched 3, which was produced from the 13C-enriched 2-13C2 solved
the assignment of the central ring carbons.

12644 J. Am. Chem. Soc., Vol. 122, No. 51, 2000
Eshdat et al.
13C2 (540 mg,73%). The product was used as a starting material for
preparing tetraphenylcyclopentadienone-13C2 without further purifica-
tion.
Experimental Section
All quantum chemical DFT calculations described herein were
performed on (B3LYP/6-31G*) level by utilizing Gaussian 98.51 The
charge distribution was calculated with NBO by using the NBO 4.052
subprogram in the Jaguar 4.053 program. The 1D and 2D NMR spectra
were recorded on a Bruker DRX-400 pulsed FT spectrometer operating
at 400.13, 100.62, and 155.51 MHz for 1H, 13C, and 7Li NMR,
respectively. Chemical shifts were measured relative to a solvent peak,
which was calibrated according to the temperature.54 Charge distribution
Tetraphenylcyclopentadienone (Tetracyclone)-13C2. The synthesis
is a modification of the literature procedure.55 The above 13C-labeled
dibenzylketone (540 mg, 2.5 mmol), benzil (540 mg, 2.6 mmol) and
2.6 mL triethylene glycol were added to a round-bottomed flask, and
gently warmed to 100 °C until the benzyl melted. 0.25 mL of trimethyl
ammonium hydroxide benzyl (40% in methanol) was added, and the
mixture was heated for 5 min. After the mixture was cooled to room
temperature, 3 mL of methanol was added, and the mixture was filtered
to give deep purple crystals, which were washed several times with
methanol until the filtrate turned purple-orange (350 mg, 35%): mp
207 °C (lit. 213-220 °C).55
in the π system was calculated out of the differences between the 13
C
NMR spectra of the neutral and the charged species using the following
equation: Qi ) (δNi - δCi)/KC, where Qi is the partial charge, δNi is
the 13C chemical shift in the neutral system and δCi is the 13C chemical
shift in the charged system of carbon i.26
1,4-Hexaphenylbenzene-13C2 (2-13C2). The synthesis is a modifica-
tion of the literature procedure.56 The above 13C-labeled tetraphenyl-
cyclopentadienone (350 mg, 0.9 mmol), diphenylacetylene (320 mg,
1.8 mmol), and benzophenone (1.7 g) were added to a round-bottomed
flask attached to an air condenser. The mixture was warmed over a
flame for 45 min and the solution turned orange-brown. Diphenyl ether
(1 mL) was added, and the solution was refluxed until all the solids
were dissolved. The product solidified upon cooling. The crystals were
washed with benzene, then filtered, and finally dried in a vacuum at
50 °C (412 mg, 89%): mp 454 °C (lit. 454-455 °C).56 Mass spectrum
major fragment at m/z (relative intensities): 537 (6), 536 (M+, 12),
Preparation of the Reduction Samples. 2 (20 mg) was added to a
5 mm NMR glass tubes with an 8-mm extension. The alkali metal (kept
in paraffin oil, cleaned from the oxidized layer and rinsed in petroleum
ether 40-60 °C) was introduced under argon to the extension as a
lithium wire or a piece of sodium. The extended tube was then placed
under high vacuum and dried by flame. In the case of sodium, the
metal was sublimed several times, creating a sodium mirror on the
8-mm extension. Approximately 1 mL of anhydrous THF-d8 (dried over
a sodium/potassium alloy under high vacuum) was vacuum transferred
to the NMR tube and was degassed several times. Finally the extended
tube was flame-sealed under high vacuum.
1
382 (36), 335 (23), 285 (26), 169 (100), 119 (62), 69 (91). H NMR
(THF-d8, rt): 6.89 m. 13C NMR (THF-d8, rt): 141.7, 141.8, 132.6,
127.6, 126.2 ppm.
Controlled Reduction Process. The reduction takes place when the
THF-d8 solution is brought into contact with the metal by inversion of
the sample and is stopped by returning the sample to the upright position
separating the metal from the solution.
9,18-Diphenyltetrabenz[a,c,h,j]anthracene (3). The reaction ap-
paratus was prepared in a manner similar to that of the reduction systems
described above except for the following: A 20 mm glass tube replaced
the NMR tube, the 8 mm extension had two narrowed necks (the lithium
wire was put in the upper part), and hexaphenylbenzene (100 mg, 0.2
mmol) was dissolved in 4 mL of anhydrous THF (dried over a sodium/
potassium alloy under high vacuum). The solution was brought in
contact with the metal for 36-48 h and turned brown. The lithium
wire was removed by sealing the lower narrowed neck, and the solution
was heated at 65 °C for 24 h. The green solution was cooled in an ice
bath and oxidized with a moderate stream of oxygen gas under an argon
funnel to give a yellow solution. The solution was extracted with
dichloromethane, which was rinsed with water, and dried. The product
was purified using a preparative thin-layer chromatography plate (silica;
hexanes/toluene 1:1). The product layer (rf ) 0.85) was extracted with
dichloromethane. A yellow powder of 9,18-diphenyltetrabenz[a,c,h,j]-
anthracene was obtained (26 mg, 27%): mp 370 °C dec UV (324, 350,
390, 413 nm) and high-resolution mass spectrometry were compatible
with the literature.45
Quench reactions. Quenching with oxygen was performed under a
nitrogen funnel. The sample was broken, and the 8 mm extension
containing the metal was removed. A mild stream of oxygen gas was
bubbled through a syringe into the cooled solution until the color
disappeared. Reaction with D2O was performed by braking the sample
in a glovebag and pouring the solution into a vial containing 5 mL of
D2O. The product was then extracted by dichloromethane and dried
over magnesium sulfate, and finally the solvent was evaporated.
Synthesis. Tetraphenylbenzene (1). The compound was prepared
according to the known procedure:15a mp 266 °C (lit. 267-268 °C,15a
268-269 °C15b). Mass spectrum m/z (relative intensities): 384(5)
383(32) 382(M+ 100) 305(10) 191(3) 183(8) (lit.15a 384(4) 382(100)
305(11) 191(7) 183(28)). 1H NMR δH (THF-d8, rt) 7.24-7.32 (m, 20H),
7.85 (s, 2H) ppm. 1C NMR δC (THF-d8, rt) 141.6, 140.3, 133.7, 130.6,
128.6, 127.3 ppm.
Dibenzylketone-13C2. The synthesis is a modification of the literature
procedure.55 R-Phenylacetic acid-13C (99.6 atom % 13C, 1 gr, 7.3 mmol)
and iron powder (150 mg) were added to a round-bottomed flask
attached to a distillation apparatus. The thermometer was in contact
with the reagents mixture, which was warmed to 320 °C. Afterward,
the thermometer was positioned over the distilled mixture. The
yellowish-brown mixture was then fractionally distilled. The fraction
boiling between 200 and 300 °C was collected to afford dibenzylketone-
NMR Data. 22-/2Li+: δH (THF-d8, 220 K) 6.42 (d, 12H, J ) 8.3
Hz, ortho), 6.55 (dd, 12H, J ) 8.3, 5.3 Hz, meta), 6.18 (t, 6H, J ) 5.3
Hz, para) ppm. δC (THF-d8, 220 K) 128.4 (ortho), 127.2 (meta), 116.4
(para), 144.9 (ipso), 117.1 (central) ppm. δLi (THF-d8, 200 K) -1.08
ppm.
2
2-/2Na+: δH (THF-d8, 220 K) 6.34 (d, 12H, J ) 7.8 Hz, ortho),
6.55 (dd, 12H, J ) 7.8, 7.0 Hz, meta), 6.16 (t, 6H, J ) 7.0 Hz, para)
ppm. δC (THF-d8, 220 K) 128.3 (ortho), 127.4 (meta), 115.8 (para),
143.8 (ipso), 117.5 (central) ppm.
(51) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.;
Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A.
D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi,
M.; Cammi, R.; Menucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.;
Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick,
D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.;
Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi,
I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.;
Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M.
W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.;
Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98; Gaussian,
Inc.: Pittsburgh, PA, 1998.
2
4-/4Li+: δH (THF-d8, 220 K) 5.56 (d, 12H, J ) 5.0 Hz, ortho),
6.25 (dd, 12H, J ) 5.0, 4.1 Hz, meta), 5.37 (t, 6H, J ) 4.1 Hz, para)
ppm. δC (THF-d8, 220 K) 121.7 (ortho), 127.3 (meta), 103.4 (para),
140.4 (ipso), 99.5 (central) ppm. δLi (THF-d8, 200 K) -1.45 ppm.
2
4-/4Na+: δH (THF-d8, 220 K) 5.35 (d, 12H, broad, ortho), 6.30 (t,
12H, broad, meta), 5.13 (t, 6H, broad, para) ppm.
2
6-/6Li+: δH (THF-d8, 180 K) 3.78 (d, 4H, J ) 4.9 Hz, ortho),
4.64 (d, 4H, J ) 4.8 Hz, ortho), 4.79 (d, 4H, J ) 5.7 Hz, ortho), 6.28
(dd, 4H, J ) 4.9, 4.5 Hz, meta), 6.35 (dd, 4H, J ) 4.8, 4.4 Hz, meta),
6.00 (dd, 4H, J ) 5.7, 4.4 Hz, meta), 4.49 (t, 2H, J ) 4.5 Hz, para)
4.55 (t, 4H, J ) 4.4 Hz, para) ppm. δLi (THF-d8, 200 K) -2.54 ppm.
(52) NBO 4.0, Board of Regents of the University of Wisconsin System
on behalf of Theoretical Chemistry Institute: Madison, WI 1996.
(53) Jaguar 4.0, Schro¨dinger, Inc.: Portland, OR 1998.
(54) The chemical shift of the solvent was measured at several different
temperatures and was calibrated relative to TMS in different concentrations.
Compare: Nir, M.; Shapiro, I. O.; Hoffman, R. E.; Rabinovitz, M. J. Chem.
Soc., Perkin Trans. 2 1996, 1607-1616.
(55) Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis; Wiley:
New York, 1968; Vol. 1, pp 198, 1149.
(56) Fieser, L. F.; Fieser, M. Reagents for Organic Synthesis; Wiley:
New York, 1968; Vol. 1, p 241.

Twist-Boat Benzene Moieties
6-/6Na+: δH (THF-d8, 180 K) 3.47 (d, 4H, J ) 8.1 Hz, ortho),
J. Am. Chem. Soc., Vol. 122, No. 51, 2000 12645
2
8.2, 6.7 Hz, meta), 5.40 (t, 2H, J ) 6.7 Hz, para) ppm. δC (THF-d8,
220 K) 130.3 (C1), 124.5 (C2), 121.4 (C3), 122.7 (C4) 129.3 (C4a),
133.4 (C8a), 136.6 (C8b), 87.4 (C9), 111.9 (ortho), 128.4 (meta), 104.3
(para), ppm.
4.55 (d, 4H, J ) 8.6 Hz, ortho), 4.81 (d, 4H, J ) 8.3 Hz, ortho), 6.19
(dd, 4H, J ) 8.1, 6.2 Hz, meta), 6.36 (dd, 4H, J ) 8.6, 5.4 Hz, meta),
5.96 (dd, 4H, J ) 8.3, 5.4 Hz, meta), 4.27 (t, 2H, J ) 6.2 Hz, para)
4.35 (t, 4H, J ) 5.4 Hz, para) ppm.
Acknowledgment. We are indebted to Dr. Elad Shabtai,
Professor Sason Shaik, Professor K. Mu¨llen, and Professor Silvio
E. Biali for fruitful discussions. We acknowledge Dr. Roy E.
Hoffmann and Dr. David Danovich for their assistance. This
research (No. 147-0) was supported by the Israeli Science
Foundation. L.E. thanks the L. Eshkol Foundation (the Ministry
of Science, Israel) for financial support. R.B. thanks the Minerva
Foundation for a postdoctoral fellowship.
3
2-/2Li+: δH (THF-d8, 270 K) 8.16 (d, 4H, J ) 8.1 Hz, H1), 7.21
(t, 4H, J ) 7.3 Hz, H2), 7.11 (t, 4H, J ) 7.3 Hz, H3) 8.45 (d, 4H, J
) 8.0 Hz, H4), 6.28 (d, 4H, J ) 8.2 Hz, ortho), 6.39 (dd, 4H, J ) 8.2,
6.7 Hz, meta), 5.56 (t, 2H, J ) 6.7 Hz, para) ppm. δC (THF-d8, 220
K) 130.2 (C1), 124.0 (C2), 121.2 (C3), 122.7 (C4) 129.6 (C4a), 133.7
(C8a), 136.4 (C8b), 86.5 (C9), 114.9 (ortho), 127.2 (meta), 106.1 (para),
ppm. δLi (THF-d8, 200 K) several lines, center of gravity: 1.45 ppm.
3
2-/2Na+: δH (THF-d8, 270 K) 8.10 (d, 4H, J ) 8.1 Hz, H1), 7.26
(dd, 4H, J ) 8.0 Hz, H2), 7.16 (t, 4H, J ) 8.0 Hz, H3) 8.52 (d, 4H,
J ) 8.0 Hz, H4), 6.09 (d, 4H, J ) 8.2 Hz, ortho), 6.30 (dd, 4H, J )
JA000072Q