478 M. Milun - N.

Trinajstiö • Cyclobutadiene, Benzocyclobutadiene, and Biphenylene

Cyclobutadiene, Benzocyclobutadiene, and Biphenylene 1

M . M il u n
The Pharm aceutical and Chemical Works
Pliva, Zagreb, Croatia, Y ugoslavia

and
N . T r in a js t iĆ
In stitute Rugjer Boskovic, Zagreb, Croatia, Y ugoslavia

(Z. Naturforsch. 28 b, 478^82 [1973]; received March 21, 1973)

A rom atic stabilization, benzocyclobutadiene, biphenylene, cyclobutadiene

T he difference in the ground state reactiv ity of cyclobutadiene, benzocyclobutadiene,
and biphenylene is a ttrib u te d to th e com bination of th eir arom atic stabilization (or
destabilization), th e presence of th e strain i th e four-m em bered rin g system , an d th e
appearance of th e localized double bonds.

Cyclobutadiene(l) and its benzo (benzocyclobuta­ It thus appears that cyclobutadiene and benzo­
diene, 2) and dibenzo-derivatives (biphenylene, 3) cyclobutadiene are far too reactive molecules to
present an interesting set of molecules to challenge have any prolonged existence. On the other hand,
both experimental and theoretical researchers. The biphenylene has been known for some time 9 and is a
schematic diagrams of these molecules are given in reasonably stable molecule10.
Fig. 1. In view of current interest 6’8>10>11»42 in cyclobuta­
diene, benzocyclobutadiene, and biphenylene che­
mistry we report our work which was carried out in
0 1 (q ju \ c o rn o ) order to understand the origin of differences in the
1 2 3
ground state reactivities of these molecules. These
differences may be attributed of the combination o f
Fig. 1. Schem atic diagram s of cyclobutadiene (1), ben­ several effects. These are the aromatic stabilization
zocyclobutadiene (2), and biphenylene (3).
(or destabilization), the presence of the strain in the
four-membered ring system and the appearance o f
For almost a century a number of organic the localized double bonds.
chemists attempted in vain, the synthesis of
cyclobutadiene2 until the preparation of the first
cyclobutadiene-metal complex (tetra-methylcyclo- Theoretical Studies and D iscussions
butadiene-nickel complex) by C r ie g e e and S c h r ö ­ a. Aromatic stabilization
d e r 3 after the suggestion by L o n g u e t - H ig g i n s and
O r g e l 4 that cyclobutadiene should form stable In order to obtain the information about the
complexes with transition metals, and the prepara­ aromatic stabilization of cyclobutadiene, benzo­
tion of free cyclobutadiene as a short lived species cyclobutadiene, and biphenylene D e w a r ’s variant 12
by W a t t s , F i t z p a t r i c k , and P e t t i t 6. The interest (variable /^-procedure13) of P o p l e SCF MO theory14,
in cyclobutadiene chemistry is still very much has been applied to this problem. This method is
present6. known16 to be very reliable for predicting the
Similarly, benzocyclobutadiene eluded synthesis ground state energy values (heats of atomization,
for a number of years 7 and so far has been detected aromatic stabilization, ionization potentials) of
only as an unstable reaction intermediate8. conjugated systems. Details of the method can be
found elsewhere15 and do not need to be repeated
here. Similarly, an extensive discussion about the
R equests for rep rin ts should be sent to Dr. N.
R ugjer Bo§kovic In stitu te, Y-41001 Z a ­
T R iN A j s T id ,
aromatic stabilization is given, for example, in ref.
greb, Croatia, Postfach 1016, Yugoslavia. 16. Note, that some recent studies17 indicated that

Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift
in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the
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 M. Milun - N. Trinajstid • Cyclobutadiene, Benzocyclobutadiene, and Biphenylene 479

there is a good correlation between the aromatic carbonyl (8.5 eV)23 closely agree with the predicted
stabilization of conjugated systems and their ther­ adiabatic ionization potential (8.58 eV) of cyclobu­
modynamic stability. tadiene.
Calculated heats of atomization, indices of aroma­
tic stabilization and ionization potentials of cyclo­ b. Calculation of bond lengths
butadiene, benzocyclobutadiene, and biphenylene The bond lengths have been calculated using the
are given in Table I. HMO resonance energies (HMO linear relation24:
D e w a r -S c h m e is in g
RE)18, REPE19, and As (HMO)20 values of 1, 2, and Lu = 1.512-0.176 p i}
3, are also indluded in Table I.
where L l} is the calculated bond length in Ä, and p ti
Results are rather interesting. All indices of
the jr-bond order between atoms i and j. The
aromatic stabilization indicate that cyclobutadiene
calculated bond lengths of cyclobutadiene and
should be unstable molecule having large conjugati-
benzocyclobutadiene are given in Fig. 2, while those
ve destabilization, while biphenylene should be
of biphenylene in Table II.
stable molecule having large conjugative stabiliza­
tion. Thus, cyclobutadiene is predicted to be 1.512X N uni
antiaromatic species, while biphenylene aromatic 1--- ---- 1
1.338X 1.379X 1.418X
species. This is, of course, in agreement with their
chemistry. Benzocyclobutadiene, on the other hand,
is predicted by REPE and As (HMO) indices to be Fig. 2. Calculated bond lengths of cyclobutadiene and
non-aromatic, and by As (SCF) index to be weakly benzocyclobutadiene.
aromatic species having a small conjugative stabili­
zation. This is also in agreement with its high The experimental values25 of biphenylene and
reactivity. some other theoretical results are also given in Table
It is interesting to note that the estimation of the II.
conjugative destabilization of cyclobutadiene was In cyclobutadiene and in the four-membered ring
attempted experimentally by B r e s l o w et al.21. system of benzocyclobutadiene the localized double
Their estimation is > 12-16 kcal/mole. Some other bonds (~1.34 Ä) are quite distinct. In biphenylene,
theoretical calculations22 gave this value as high as of course, there is no possibility of forming the ex­
33 kcal/mole. This may be a question of academic ternal localized double bonds in four-membered ring.
interest, however, it is certain that conjugative The appearance of localized double bonds in
destabilization in cyclobutadiene is very large. cyclobutadiene and benzocyclobutadiene causes that
Perhaps of the same absolute magnitude as the these molecules have ideal geometries for D iels-
conjugative stabilization in benzene (20.0 kcal/ A ld er reactions. Thus, both molecules elude isola­
mole)12. Hence, cyclobutadiene should be thermodi- tion as stable substances, because in absence of
namically highly unstable species as it is the case. other reagents with which they can react they un­
Experimental ionization potentials of these com­ dergo D ie ls-A ld e r dimerization giving unstable
pounds are not known. Some estimates from the adducts which then isomerize to more stable dimers26.
photoelectron spectrum of cyclobutadiene-iron tri­ Similarly, phenyl-derivatives of cyclobutadiene (o-

Table I. Calculated heats of atom ization (A H a25 °C), indices of arom atic stabilization, and ionization potentials
(IP).

Molecule z!Ha250C HMO R E As[SCF] R E P E (ß )19 As[HMO] I P (eV)

(eV)12 OS)18 (kcal/mole) (ß)
Cyclobutadiene 36.75 0.00 -1 8 .0 30 -0.268 -1.04 v:8.6730*
a:8.58
Benzo-Cyclobutadiene 70.88 2.38 8.1 -0.027 -0.22 8.43
Biphenylene 104.87 4.50 31.012 0.027 0.33 8.34

♦This is in a good agreem ent w ith th e value (8.50 eV) estim ated from th e photoelectron spectrum of cyclobuta­
diene iron tricarbonyl23.
480 M. Milun - N. Trinajstiö • Cyclobutadiene, Benzocyclobutadiene, and Biphenylene

diphenylcyclobutadienes) have been trapped with Calculated bond lengths of benzocyclobutadiene

powerful dienofile tetracyanoethylene 27 giving two and biphenylene indicated that 2B and 3A are their
adducts: predominant forms. Recently, we have developed a
,CN
theoretical index named K e k u l 6 index which
>-CN defines the order of the relative importance of
1 various valence bond structures of conjugated
\~C N / CN
CN HjC, ^ polycyclic systems28. K e k u l 6 indices (K) can be
Another interesting point is worth mentioning calculated for individual valence structure (L ) from
here. Three K e k u l 6 structures can be written for given molecular orbital wavefunction using expres­
benzocyclobutadiene. Similarly, five canonical sion:
forms can be written for biphenylene. Two K ekul£ K(L) = Z [?i + ?! + P»]112
structures of cyclobutadiene are, of course, identi­ 2N («,j)e l
cal. K ek u lä structures of cyclobutadiene (1A, IB), where q\ and q) are ^-electron charge densities on
Benzocyclobutadiene (2A, 2B, 2C), and biphenylene atom i and j, while pi\ is the corresponding n-bond
(3A, 3B, 3C, 3D, 3E) are given in Fig. 3. order. Various K e k u l 6 structures of a particular
polycyclic molecule can be than ordered according
O to the magnitude of this index.
1A 1B The structures with the largest index corresponds
0.866 0.866 to K eku 16-type structure with the greatest number
of formal benzene K e k u l 6 formula, i.e. to a
structure which the empirical F r i e s rule29 predicts
as the most stable. The values of K e k u l 6 index for
Q a C d
valence structures of cyclobutadiene, benzocyclobu­
2A 2B 2C
0.905 0.941 0.832 tadiene, and biphenylene are also given in Fig. 3.
These results also indicate 2B and 3A as the
0=0 3A
0.918
0=0 0.895
3B
predominant K e k u l 6 forms of benzocyclobutadie­
ne and biphenylene*.

c. Strain energies
C n3C O 0 =3D 0 The ring strain of the four-membered ring has
0.906
been approximatively estimated using the modified
0.906
D a u b e n ’s formula17:
Strain energy = \ \ 2 A £ (Aon)
0 =3E 0 i
0.865 Where Aai is the angle strain at the atom i. The
Fig. 3. K e k u le structures and K e k u le indices. summation goes over all atoms within the particular
T able II. Calculated bond lengths in biphenylene by various authors.
BO N D L E N G T H [A]
BOND C a lc u late d
E xperim ental25 A li and Coulson 43 Skancke 44 W arren and V B46 O ur result
Yandle 45

1-2 1.423±0.003 1.408 1.421 1.413 1.38 1.409

1-10 1.372±0.002 1.395 1.379 1.385 1.41 1.386
2-3 1.385±0.004 1.394 1.375 1.385 1.41 1.385
9-10 1.514±0.003 1.467 1.509 1.476 1.45 1.485
10-11 1.426±0.003 1.414 1.417 1.422 1.41 1.412

* Note added in proof: R ecent m axim um overlap calculations (M. R a n d i <5 and Lj. V u jisid , J. org. C hem istry
37, 4302 [1972]) reached the same result, th e structures 2B and 3A being energetically th e m ost favoured.
 M. Milun - N. Trinajstiö • Cyclobutadiene, Benzocyclobutadiene, and Biphenylene 481

ring. A is a constant (0 .0 2 4 kcal/deg2) obtained version of their variant of the SCF MO theory13»37,
considering experimental energies of monocyclic arrived to the value of 27.5 kcal/mole. C a ss, S p r in g -
olefins and paraffins. The strain angle in the a l l , and Q u in c e y 38 obtained a value of 59+5 kcal/
polycyclic conjugated hydrocarbons represents the mole comparing the heats of formation of biphenyle­
angle distortion from 120°. Only carbon skeleton of ne and biphenyl. Some of these results differ
a molecule is taken into account. Calculated angles considerably from our values (86,79 kcal/mole). It is
in the four-membered rings of cyclobutadiene, difficult to say how far our results are from the truth
benzocyclobutadiene, and biphenylene are given in but some experimental results show39 that the four
Fig. 4. membered ring in biphenylene can be ruptured
W a6° - ^ 1 5 0 ° [ K 7 .8 ° ] although under the fairly vigorous conditions.
Ao°
Conclusions
Apparently there are mainly three effects (aroma­
Fig. 4. Calculated angles in th e four-m em bered ring. tic destabilization, appearance of localized double
E xperim ental angles (ref. 25) of biphenylene are given bonds, ring strain) responsible foi different ground
in brackets.
state stabilities of cyclobutadiene, benzocyclobuta­
Experimental angles25 of biphenylene agree quite diene, and biphenylene. The degree of stability
well with the calculated values. depends on how many of these effects are combined
The calculated strain energies are given in Table in particular molecule. These can be seen in Table
III. IV.
Table I I I . S train energies in the four-m em bered ring T able IV. Com bination of effects responsible for lower
system s. stability.

Compound S train energy [kcal] Molecule Effects responsible for lower stab ility
Cyclobutadiene 43 A rom atic Localised Ring
destabili­ double bond strain
Benzocyclobutadiene 57 zation
Biphenylene 86 [79]* Cyclobutadiene + + +
* This value is obtained w hen th e experim ental angles Benzo­ — + +
are used. cyclobutadiene
Biphenylene — — +
In literature there are scarce data about the strain
in the four-membered ring of cyclobutadiene,
The prediction extracted from Table IV nicely
benzocyclobutadiene and biphenylene. The earlier
parallels the experimental facts. The case of naphto-
estimate of the ring strain of cyclobutadiene is far
(a) cyclobutadiene and naphto(b) cyclobutadiene
too low (19 kcal/mole)30. However, this is not
which are a closely related isomers of biphenylene
suprising because the M IN D O /2 version31 used in
shows that our results may have certain practical
the above work80 underestimates the strain energy
use.
in strained ring systems for approximatively 20
kcal/mole32. The strain energy in cyclobutadiene
with this correction (40 kcal/mole) is then close to OCa
our value (43 kcal/mole). The strain energy in the The appearance of localized double bond in
four membered ring of benzocyclobutadiene is not addition to the ring strain make these molecules
known although it was suggested33 that the strain much less stable then biphenylene. In fact, the
energy might be higher than 50 kcal/mole. Several chemistry of naphto(a)- and naphto(b)-cyclobuta­
researchers tried to estimate the ring strain in the diene is closely related to benzocyclobutadiene
four-membered ring of biphenylene. C o u ls o n 34 chemistry and thus, both molecules have only been
estimated this strain to be 100 kcal/mole. Later, observed as unstable intermediates10-40.
C o u ls o n and M o f f i t 35 calculated it to be 7 4 kcal/ It is interesting to note that recently developed41
mole. D e w a r and G l e i c h e r 38, using the earlier topological expressions for total ^-energy of conju­
482 M. Milun - N. Trinajstid • Cyclobutadiene, Benzocyclobutadiene, and Biphenylene

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(e.g.