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Mechanistic Organic Photochemistry.

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JANUARY 1 9 6 9
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Mechanistic Organic Photochemistry
By N.E. ZimmermanI*l
Organic photochemical reactions can be understood as transformations oj the electronically excited states of the reactant molecules. By considering Lewis strucrure or molecular orbital representations of these excited states ir is possible to outline the several
possible reactions available in the case of a given reactant. A number of different types
of photochemical transformations are now reasonably well undersrood. In these cases
one finds the same common controlling fearure, namely the tendency for an excited state
species to follow mechanistic pathways of minimum energy and The requirement for continuous elecrron redistribution in following these path ways. These preferred transformations can often be selected by inspection of relative bond orders for diferent types of
bonding, by comparison of the potential energy surfaces available to the excited state
molecules, arid by use of correlation diagrams. The reactions derive from both singlet
and triplet states, and one of the more reliable methods now available for identifving
excited states reacting is termed the 'Ifirgerprint method". Examples of the author's
mechanistic approach are given both for ketone and for hydrocarbon photochemistry.
(AO's) available at the different atoms and is really a
three dimensional Lewis structure.
1. Introduction
In 1961 we noted[ll that, despite the high energy
employed in photochemistry, the molecular transformations encountered are generally very selective.
The excited state molecule seems to transform itself
in such a way that electron localization is minimized.
We suggested that by use of simple Lewis structure
and molecular orbital representations, one could
often predict and understand the reaction route
chosen by the electronically excited state of reactant.
Subsequent to this we investigated the applicability
of our proposal to a number of photochemical reactions. The present article summarizes some of these
2. Molecular Orbital and Resonance Methods of
Representing Excited States
The carbonyl group is especially useful in illustrating
the two most important types of electronic excitation,
n--x* and x--x*. Figure 1 shows the atomic orbitals
(1) (AO)
Fig. I . Ground state ( I } of carbonyl group. n-x* excited state resonance contributors (Za) and (26). 0 represents spn hybrid electrons;
y's, py electrons; 0 , n-system electrons. A 0 signifies atomic orbital
In this representation there is a low energy sp" hybrid orbital on oxygen coaxial with the sigma C - 0
bond and containing two electrons, a p,, non-bonding
orbital containing two electrons in the ground state,
and lastly a x-system deriving from interaction of two
px orbitals.
n-x* excitation promotes a py electron to the x-systen. In resonance terminology, two contributors
result from our being able to write the promoted
electrons as in the carbon or the oxygen px orbital.
The molecular orbital equivalent picture (Fig. 2 )
differs only in that the two molecular orbitals (the
[*I Prof. Dr.
Howard E. Zimmerman
Chemistry Department
University of Wisconsin
Madison, Wisconsin 53706 (USA)
Angew. Chem. internat. Edit.
/ Vol. 8 (1969) 1 No. I
[l] H . E. Zimmerman, Abstracts of the 17th National Organic
Chemistry Symposium of the Amer. chem. SOC.,Bloomington,
Indiana, June 1961, p. 31.
MO’s) derived from overlap of the two pn orbitals are
depicted explicitly. In the ground state the x MO is
doubly occupied but the x * MO is vacant. In the
n-x* excited state, a p, electron has been promoted
to the antibonding (i.e. x * ) MO.
way of the n-x* triplet excited state of the reactant,
and this evidence is now summarized.
First of all, sensitization with acetophenone absorbing
essentially all of the incident light gives the same
quantum yield within experimental error (i.e.@ = 0.81).
This finding can be reasonably interpreted to mean
that both reactions involve the same excited state, the
triplet (see Scheme 1).
i . c.
Fig. 2. Molecular orbital representationof n-n* and n-n* excitation
of ( I ) to (2) and (3). respectively.
The n-x* excited state results on excitation by ultraviolet light of ca. 300 nm (depending on exact structure) where there is a weak absorption band in ketones.
A second excitation process may be seen to be possible, one in which a x-MO electron is promoted to the
x * orbital. This is termed x-x* and arises usually by
irradiation at shorter wavelengths where there is the
intense absorption band whose position follows
Woodward’s rules. In two dimensions n-x* excitation
can be represented as in Fig. 3.
Fig. 3. Two dimensional representationof n-n* excitation.
Scheme 1. “Type A” rearrangement of 4,4-diphenylcyclohexadienone.
The proposed mechanism of rearrangement is indicated by solid arrows.
Potentially available pathways not utilized are shown by dashed arrows.
The ground-state species are given in the bottom row. and above each
ground-state species is drawn the corresponding n-n* excited state.
Intersystem crossing occurs between (41 and (61,and between (7) and
(9). The excitation energy gained on going from (41 -+ 161 is Iost
during the step (7) -+ (9).
The evidence in favor of loss of electronic excitation prior to
complete skeletal rearrangement is twofold. First, the triplet
excited state (8) of 6,6-diphenylbicyclo[3.1.0]hex-3-en-2-one
(5) exhibits behavior, when independently generated, which
is not found in low conversion photolysis runs beginning
with 4,4-diphenylcyclohexadienone (4) 133. Secondly, the
mesoionic zwitterion (9) has been independently generated
in research by Dopp 141 and does indeed afford 6,6-diphenylbicyclo[3.1 .O]hex-3-en-2-one ( 5 ) providing necessary evidence for the zwitterion being an intermediate in the photochemical rearrangements as postulated (see Scheme 2).
3. Cyclohexadienone Photochemistry
One of the most intriguing photochemical transformations is the “Type A ” [ z J rearrangement of
cyclohexadienones. An example which has been of
considerable interest to us is the case of 4,4-diphenylcyclohexadienone ( 4 ) which affords 6,B-diphenylbicyclo[3.1 .O]hex-3-en-Z-one (5).
Scheme 2. “Photochemistry” without light (route b is not observed).
It was found that the reaction is unusually efficient
with a quantum yield of 0.85 moles/Einstein[*l.
Evidence was advanced that the reaction proceeds by
There are three interesting facets of the reaction ( 4 ) +
(5). One concerns the underlying reasons for the
initial 3,s-bonding in the n-x* excited state of dienone. Reference to Fig. 4 shows the increased 3,s-bond
[2] a) H. E. Zimmerman and D. I. Schuster, J. Amer. chem. SOC.
83,4486 (1961); b) 84,4527 (1962).
[*I An Einstein is defined as 6.023 x 102 quanta and corresponds to one “mole” of light.
[31 H. E. Zimmerman and J. S. Swenton, J. Amer. chem. SOC.,
89, 906 (1967).
[41 H. E. Zimmerman, D. Dopp, and P. S. Huyffer, J. Amer.
chem. SOC.88, 5352 (1966).
Angew. Chem. internat. Edit.
Vol. 8 (1969) No. 1
n-T*- excitation with enhancement of
6. p-bonding
--tt- n
?r-.rr*-excitation with no enhancement of
p. p-bonding
dently [4bl. Of two possible stereochemical courses for
the reaction (10) --f (9) + ( 5 ) , a pivot mechanism involving bond (C-l)-(C-6) breaking with pivoting
about bond (C-5)-(C-6) and formation of bond (C-4)
to (C-6) and a “slither” mechanism in which C-6
migrates from C-5 to C-4 and then from C-1 to C-5,
only the latter occurs. The preferred process is
equivalent to an inversion of configuration at C-6
with bond (C-l)-(C-6) breaking as (C-4)-(C-6)
forms and with (C-5)-(C-6) remaining intact. This
preference has been rationalized on two bases, one of
which is touched upon briefly later in this article (see
Section 8 and Fig. 15c).
Fig. 4. Molecular orbital representation of n--x* and n-n* excitation
processes for cyclohexadienones. H,wave function positive. 0, wave
function negative.
order resulting on n-x* excitation 131. The second
point involves the question why the zwitterion (9)
rearranges so efficiently to the bicyclic ketone ( 5 )
(process a in Scheme 2) rather than reverting to the
dienone ( 4 ) (process b, Scheme 2). The latter process
is one which an organic chemist might consider as a
reasonable a priori possibility. The correlation diagram (Fig. 5 ) shows that reversion to the dienone ( 4 )
is forbidden by symmetry; without change in electron
population an exceedingly high energy doubly excited
state would result 131.
The third point of interest concerns the stereochemistry of the Type A rearrangement as observedL4al in
the non-photochemical approach to zwitterion (9).
When (IOa) or (lob) - having two different aryl
groups at C-6 - was allowed to react with potassium
tert-butoxide, the group initially exo remained exo in
the product and the endo group was still endo in the
product. This finding has been confirmed indepen[4] a) H. E. Zimmerman and D . S . Crumrine, J. Amer. chem. SOC.
90, 5612 (1968); b) T . M. Brennan and R. K . Hi& ibid. 90, 5674
Angew. Chem. internat. Edit. / Vol. 8 (1969) / N o . I
Fig. 5. MO correlation diagram for closure of dienone to 3,5-bridged
wave function negative. f o r 1,
species. H,wave function positive; 0,
electrons in levels occupied in dienone n-n* triplet. 0 ,electrons in levels
occupied in ground state zwitterion. D, dienone. Z, zwitterion.
A related rearrangement is the Type B transformation
of bicycl0[3.l.O]hex-3-en-2-ones to phenols. Thus the
bicyclic ketone ( 5 ) gives 2,3-diphenylphenol and some
3,4-diphenylphenol on irradiation. The mechanism
proposed is given in Scheme 3. In agreement with
and Wilson15al suggested that removal of the second
double bond enforces the phenyl migration and that
the phenyl migration type rearrangement is less efficient than the dienone Type A process. This prediction was confirmed by quantum yield studies by Zimmerman and Hancock [61.
Quantum yields for unsensitized reaction :
@ = 0.043 0.043 0.0003 0.0002
Quantum yields for reaction sensitized by propiophenone:
@ = 0.040 0.039 0.0003 0.0002
Scheme 3. Type B rearrangement of 6,6-diphenylbicyclo[3.1.O]hex-3en-2-one. Electron demotion occurs between (12) and (13). The dashed
arrows indicate processes that have not been observed. Intersystem
crossing takes place on going from (S) to (8) and from (12) to (13).
the picture of the zwitterion (13) rearranging and not
the diradical-like excited state (12), it was found by
Grunewaldtsl that 6-p-cyanophenyl-6-phenylbicyclo[3.1 .O]hex-3-en-2-one (16) gives mainly 2-phenyl-3-pcyanophenylphenol ( I 7) but no p-cyanophenyl migration product (see Scheme 4).
Scheme4. Test for six-ring zwitterion in the reaction (16) + (17).
Whereas the cyanophenyl group would migrate in the biradical (19).
the phenyl group would migrate in the zwitterion (20).
p-Cyanophenyl should migrate preferentially to an
odd electron site while phenyl should migrate to an
electron deficient center. The use of migratory aptitudes in photochemistry to determine the nature of
the rearranging species is considered again later.
4. The Aryl Migration Reaction of
Irradiation of 4,4-diphenylcyclohexenone (21) leads
to phenyl migration products (see Scheme 5). Since in
the photolysis of 4,4-diphenylcyclohexadienone ( 4 )
(Type A transformation) such phenyl migration is an
a priori possibility which does not occur, Zirnrnerman
[ 5 ] H. E. Zimmerman and J. 0. Grunewald, J. Amer. chem. SOC.
89, 3353 (1967).
[5a] H. E. Z i m m r m a n and J. W.WiIson,J. Amer. chem. SOC.86,
4036 (1964).
Scheme 5. Examples of the fingerprint method applied to the irradiation of 4,4-diphenyIcyclohexenone (21) to give (22), (23), and (24).
The quantum yield measurements were obtained by inverse
isotope dilution. This method has the advantage of great
sensitivity so that reactions can be run to conversions as low
as 1% with even relativeIy Iow quantum yields; this allows
one to be certain that products are not competing for light.
Inspection of the quantum yields (see Scheme 5 ) with
and without sensitization shows that the same distribution of efficiencies is obtained on direct irradiation
as in the sensitized ones where one is dealing with
preformed triplet excited state. The product and quantum yields distribution can be used as a “fingerprint”,
and the direct irradiations have the same fingerprint
as those beginning with the triplet. This “fingerprint
method” of demonstrating the intervention of triplet
excited states is one of the more reliable tests available
to the photochemist, and in the present case it shows
that the direct irradiation of 4,4-diphenylcyclohexenone (21) leads to products by way of the triplet excited state.
A second aspect is of interest, namely the high stereoselectivity favoring formation of the trans isomer
(22) *I of 5,6-diphenylbicyclo[3.1 .O]hexan-2-one by
a factor of 14O:l over cis (23). This stereochemical
preference is not just a matter of mutual avoidance of
two phenyl groups due to van der Waals forces, since
in the trans isomer the endo-phenyl-five-ring interaction
is just as severeas the phenyl-phenyl hindrance in thecis.
This stereochemistry seems to arise from a 2,4-bonding
to form the three-membered ring concerted with phenyl
migration from C-4 to C-3 with inversion of configuration at C-4 (see Fig. 6).
In this process there is a disrotatory motion about
bonds (C-l)-(C-2) and (C-4)-(C-5) to form the new
internal three-ring bond; the net effect is one phenyl
above the new three ring and one below.
It is generally insufficient merely to look at relative
quantum yields in order to compare the facility with
which two reactions proceed. Actually, one needs the
[6] H. E. Zimmerman and K. G . Hancock, 3. Amer. chem. SOC.
90,3749 (1968).
[*] trans with respect to the phenyl groups on the three-membered
Angew. Chem. internat. Edit. 1 Vol. 8 (1969) 1 No. I
Table 1. Efficiencies and rates of triplet rearrangements of cyclohexenones and cyclohexadienones.
Type rearrangement
kr (sec-1)
4,4-diphenylcyclohexadienone (‘4)
4,4-diphenylcyclohexenone (21)
3.8 x 107
2.9 x 105
4a-methyl-Z,3,4,4a,9,10- Type A
gests that the potential energy surfaces surrounding the
excited states may be similar to ground state surfaces.
Also of interest in connection with the photochemistry of
f 22)
Fig. 6.
The stereochemical course of aryl migration during the reaction
(22) with inversion of configuration at C-4 (cyclohexane num-
rate at which the excited state reacts. One can obtain
the rates of triplet state rearrangements from SternVolmer plots (see Fig. 8) by a method discussed below.
4,4-Diphenylcyclohexenone provides an example (note
Fig. 7). Here the triplet rate was found t o be kr =
3.8 x lo7 sec-1[61. Although this is a very fast reaction
cyclohexenones is the matter of migratory aptitudes. In both
the rearrangements of 4,4-diarylcyclohexenones,such as
(27) [71, and 4,4 - diary1 - 1,4 - dihydronaphthalenones, e.g.
(32) [81, it has been found that cyanophenyl migrates with
greater efficiency than phenyl. This tells us that the P-carbon
(i.e. C-3) of the electronically excited enone moiety is not
electron deficient, since phenyl migrates preferentially to
positive centers. Additionally, when the competition is between phenyl and anisyl, we find that it is anisyl whose
migration is preferredr7.91. This result tells us that the @carbon cannot be heavily electron rich in the excited state
100 I
l 257
101 -+
Fig. 7. Stern-Volmer plots of the reciprocal of the quantum yield
against the quencher concentration [Q] (mole/l). Variation of quenching
rate with triplet energy of quencher for 4,4-diphenylcyclohexenone (21).
Quenchers: - - cyclohexadiene. -A-, dimethylhexadiene.
1,3-pentadiene. -0-, naphthalene.
compared to the ground state rate constants, it is slow
compared to the lower limit of k, 2 1010 sec-1 found
for the rearrangement of the triplet excited state of
4,4-diphenylcyclohexadienone (6). Thus the phenyl
migration reaction does appear to follow a higher
energy pathway than the Type A rearrangement of
dienones. Yet the rearrangement of the triplet of ( 2 I )
is faster than the Type A rearrangement of 4-alkylcyclohexenones such as ( 4 4 ) ; and it has been proposed
that this rearrangement fortuitously effects the same
skeletal change as the Type A dienone rearrangement
without having a similar low energy pathway. The
relative efficiencies and rates of the three types of rearrangement are summarized in Table 1.
Very recently evidence has been obtained by Elser
that the reaction in Scheme 5 has an appreciable
activation energy (ca. 10 kcal/mole) for excited state
rearrangement and that the activation process has a
“normal” frequency factor (about 1014-5). This sug[6a] H. E. Zimmerman and W. R. Elser, J. Amer. chem. SOC.,
in press.
Angew. Chem. internat. Edit. / Vol. 8 (1969) 1 No. I
f 35)
(a), Ar = p-CN-C6H4
(b), A r = p-CH30-C6&
Scheme 6.
Migratory aptitudes.
171 H. E. Zimmerman, R . D. Rieke, and J. R . Scheffer, J. Amer.
chem. SOC.89, 2033 (1967).
181 H. E. Zimmerrnan, R. C. Hahn, H. Morrison, and M . C.
Wani, J. Amer. chem. Soc. 87, 1138 (1965).
[9] H. E. Zimmerman, R . Nasielski, and A. Guimanini, unpublished.
either, since anisyl would not elect to migrate to a negative
center in preference to phenyl. One further point is that one
might have attempted to explain the preferential migration
of cyanophenyl over phenyl by the rationale that migration
is to a positive center but that stabilization by the group
remaining behind and not migrating is the controlling factor.
However, in such a case anisyl would remain behind and this
is not observed. The conclusion is that the excited state rearrangement can be pictured as a migration to an odd electron center (see Scheme 6 ) .
Also recently evidence has been uncovered showing
that not only the quantum yield for the reaction of
4,4-diarylcyclohexenones is increased by introduction
of ap-cyano group but also the rate of triplet rearrangement is enhanced (by a factor of ca. 1 2 ) [ 9 a l . The p cyano group, however, does not appreciably affect the
rate of excited state decay; this suggests that rearrangement and decay processes have little in common.
5. The Type A Rearrangement of Cyclohexenones
type discussed in the previous section occurred as a
minor reaction (see Scheme 7).
It was mentioned that 2-(cis-styryl)-3-phenylcyclobutanone (43) was a product of the reaction as well.
(The intermediate (38) in Scheme 7 is just the bridged
version of the same biradical (38) shown in Scheme 8
Scheme 8.
A second type of enone transformation is known.
Skeletally, this is of the Type A variety; however,
mechanistically it is quite different from the Type A
dienone rearrangements. An example of the Type A
enone rearrangement is the photochemical transformation of 4,5-diphenylcyclohexenone(41) to afford
4,6-diphenyIbicyclo[3.l.O]hexan-2-one (40) along
with 2-(cis- styry1)-3 - phenylcyclobutanone (43) [lo].
Although the same product (40) would arise by the
phenyl migration mechanism discussed in the previous
section, the mechanism of the rearrangement was
established as Type A by following a C-14 label
originally placed at C-3 in the 4,5-diphenylcyclohexenone (41); the label was found at C-4 (cyclohexane numbering) to the extent of 98.5 % showing a
heavy predominance of a Type A skeletal transformation. Since 1.5% of the C-14 label originally at C-3
did remain at C-3 (cyclohexane numbering), it was
concluded that a phenyl migration mechanism of the
Mechanism of cyclobutanone formation [lo].
as open for simplicity.) The alternative mode of reaction in which the benzylic radical in (38) attacks C-2
rather than C-3 can be seen to afford the observed
cyclobutane product (43).
It may be noted in Scheme 7 that the phenyl migration
route leads to intermediate species (42) in which there
is an odd electron localized on C-4, a carbon not bearing a phenyl group. This contrasts with the situation
in the rearrangement of 4,4-diphenylcyclohexenone
where after phenyl migration any free valence on C-4
is stabilized by a phenyl located at this carbon and not
migrating. As a consequence one can understand
phenyl migration being preferred in the photolysis of
4,4-diphenylcyclohexenone (21) while the Type A
enone rearrangement is preferred in the case of 4,5diphenylcyclohexenone ( 4 I ) .
It appears that the Type A rearrangement of cyclohexenones takes precedence over the phenyl migration
r \
( 00 L
(40), 1,5%
Scheme 7. Competitive pathways for 4,5-diphenylcyclohexenonerearrangement [lo]. Upper row, Type A route. Lower row, phenyl migration. *C,14C label.
when there is insufficient stabilization by the group
not migrating in the aryl migration; with one phenyl
group and one alkyl group at C-4 this seems to be the
One example of interest is the rearrangement of 4amethyl-2,3,4,4a,9,10-hexahydro-2-phenanthrone(44)
to the tetracyclic product (45) rI1J. In this case the reaction was shown to proceed by way of the triplet
[9a] H. E. Zimmerman and N . Lewin, J. Amer. chem. SOC., in
[lo] a) H. E. Zimmerman and D. .I
. J . Amer. chem. SOC.
88, 4114 (1966); b) ibid. 88, 4905 (1966).
Angew. Chem. internat. Edit.
1 Vol. 8 (1969) J No. I
excited state since the quantum yield on acetophenone
sensitization (0= 0.00086) is the same within experimental error as that on direct irradiation (@ =
0.00084) [Ill. This is a case of fingerprint identification
with “only one finger” employed and is not totally
satisfactory since it is conceivable that the singlet and
triplet might accidentally rearrange with the same efficiency. Quenching experiments proved useful in
dispelling any doubt. These are represented in Fig. 8
where the reciprocal of quantum yield is plotted
versus the concentration of naphthalene and di-tertbutylnitroxyl quenchers [111. The rationale for the
Stern-Volmer plot can be seen in equation (2).
900 -
look at systems lacking non-bonding electrons and
therefore having only -x--x* excited states. One example studied was the methylene analog (49) of 4,4diphenylcyclohexadienone ( 4 ) [121.
When l-methylene-4,4-diphenyl-2,s - cyclohexadiene
(49) was irradiated, the initial product was the bicyclic product (SO). The reaction quite clearly involves phenyl migration rather than a Type A rearrangement and hence contrasts with the behavior of 4,4-disubstituted cyclohexadienones. When a high energy
photosensitizer is used, there is virtually no reaction,
although the triene (49) quenches the benzophenonebenzhydrol reaction. The quenching of the benzophenone-benzhydrol reaction shows that triplet energy
transfer from benzophenone to (49) is effective. The
lack of product from (49) under these conditions
shows that the triene triplet is unreactive. The rearrangement on direct irradiation then must result from
the singlet excited state (see Scheme 9) 1121.
100 /
only triplet processes
leading to product
In equation (2), [TI is the concentration of triplet
excited state, [Q] is the concentration of triplet
quencher, and k d is the rate constant for triplet
deactivation. Equation (2) results from the definition of
quantum yield, namely the ratio of the rate of product
formation from an excited state to the sum of all possible rates of excited state disappearance. It can be seen
that the reciprocal of quantum yield then is linear
with the concentration of quencher, and that the slope
of this plot is equal to the rate constant for quenching
divided by the rate constant for triplet rearrangement.
Where quenching is controlled by diffusion, one can
substitute the known rate constants for diffusion into
equation ( 2 ) for k, and then, knowing the slope, solve
for k,.
6. Methylene Analogs of Dienones and Enones
Because the photochemistry of the dienones and enones studied was postulated to be characteristic of
n--x* excited states and to derive from a x-system
having one extra electron, it seemed of interest to
1111 a) H . E. Zimmerman, R . G. Lewis, J . J. McCullough,
A . Padwa, S . Staley, and M . Semmelhack, J. Amer. chem. SOC.
88, 159 (1966); b) ibid. 88, 1965 (1966).
Angew. Chem. internat. Edit. J Vol. 8 (1969) 1No. I
Scheme 9.
Rearrangement of l-methylene-4,4-diphenyl-2,5-c~clohexadiene (49).
One especially interesting aspect of the photochemistry
observed is the failure of the triplet, or singlet for that
matter, of (49) to bond between C-3 and C-5; such
bonding is common and facile for the corresponding
dienones. However, in the case of the dienones ( 4 )
such bonding is expected for the n-x* excited states
on the basis o f a high positive bond order between
C-3 and C-5. In contrast, for the -x-x* excited state of
the triene (49) the bond order is zero in the Huckel
approximation. Hence the lack of such bonding and
of a Type A rearrangement is not unreasonable.
Another case of interest is the methylene analog (51)
of 4,4-diphenylcyclohexenone (21) 1131. Here, irradiation of 1-methylene-4,4-diphenyl-2-cyclohexene( S l )
leads to phenyl migration and t o formation of the two
stereoisomers of 2 - methylene - 5,6 - diphenylbicyclo[3.1.0]hexane (53) (major product) and (52) (minor
product). Again the reaction is found to be a singlet
one; and the triplet, once formed, is unreactive.
The mechanism envisaged is very similar to that of
triene (49). We note that the stereochemistry is the
[12] H. E. Zimmerman, P. Hackett, D . F. Juers, and B. Schroder,
J. Amer. chem. SOC.89, 5973 (1967).
[13] H . E. Zimmerman and G. E . Samuelson, I. Amer. chem.
SOC.89, 5971 (1967).
on barrelene, semibullvalene, and on each of the intermediate species utilized in the two mechanisms [Is].
Thus the ground state and first excited state energies
of reactant and each molecular species along the reaction coordinate of each mechanism was obtained.
For geometries in between those of biradical species
same as that of the 4,4-diarylcyclohexenones,e.g. (21),
with the trans-product being preferred, giving weight
to the view that this stereochemical course is general.
7. Further x-IT* Photochemistry
An especially intriguing photochemical reaction is the
transformation of barrelene (54) to semibullvalene
(55). Since acetone sensitization is necessary for the
reaction, we can conclude that a triplet excited state
of barrelene is the rearranging species [141.
(55) (la,O P , 17) (55) (2a, OP, 0 4
Two fundamentally different mechanisms seemed
possible for this transformation (see Scheme 10). A
method of differentiating between these was available [I53 which depended on the fact that semibullvalene
undergoes exceedingly rapid valence tautomerism as
shown in eq. (4) and as a consequence shows only
three peaks in the NMR, those due to the alpha, beta,
and gamma type hydrogen atoms (see eq. (4) for
labeling) C14J.
By photolysis of barrelene in which the vinyl hydrogen
atoms were replaced by deuterium it was possible to
follow the disposition of the remaining, bridgehead
hydrogen atoms after irradiation. The labeling expected for the two mechanisms is seen in Scheme 10. Mechanism I predicts that the two hydrogen atoms will be
located at alpha positions and that only this peak will
be seen in the product NMR spectrum. Mechanism I1
predicts a distribution of 75 % alpha, 0 % beta, and
25% gamma hydrogen atoms; and it is this which is
observed experimentally 1151. This prediction, however, is dependent on the triplet biradical (58) being a
discrete intermediate with finite lifetime and thus symmetrical; the symmetrical allylic biradical (58) would
bond at either allylic position with equal probability [*I. That the allylic biradical should have an appreciable lifetime is not surprising since it must arise
from a triplet and would seem likely itself to be a
triplet with intersystem crossing being necessary before collapse to product is possible.
In an attempt to understand the preference for Mechanism 11, three-dimensional Hiickel theory was utilized
[14] H. E. Zimmerman and G . L. Grunewald, J . Amer. chem. SOC.
88, 183 (1966).
[15] H. E. Zimmerman, R. W. Binkley, R. S. Givens, and M . A.
Sherwin, J. Amer. chem. SOC.89, 3932 (1967).
[*] This assumed negligible secondary isotope effects.
Scheme 10. Possible mechanisms for the barrelene (54) to sernibullsignifies H label: deuterium elsewhere.
valene (55) interconversion
which can be written explicitly, the geometry was taken
to be intermediate. From such calculations one
obtains cross-sections of potential energy surfaces for
the ground and excited states. These are depicted in
Figs. 9a and 9b.
1551 1541
Figures 9a, 9b. Potential energy vs reaction coordinate for mechanisms
I and 11, respectively. -0-, ground state curve. ---, excited state curve.
Mechanism I (Fig. 9a) leads on excitation to a species requiring quite a n appreciable activation energy to bridge
concertedly to give biradical (56). On the other hand, the
ground and excited state surfaces for mechanism I1 (Fig. 9b)
are such that the vertically excited molecule ( i e . excited
without change in geometry) is on a slope and has enough
vibrational energy to surmount the barrier leading to the
main excited-state minimum. This minimum is positioned
above a n electronic ground state minimum which leads
preferentially to the product semibullvalene rather than back
to barrelene. In agreement with this view is the failure to
observe any barrelene from the irradiation of semibullvalene.
Although these three dimensional calculations are approximate and mainly of qualitative use, they present a starting
point for considering the photochemical reactivity of molecules undergoing complex transformations.
Angew. Chem. internat. Edit. [ Vol. 8 (1969) [ N o . I
In connection with the barrelene ( 54) to semibullvalene ( 5 5 ) conversion, it is of interest that semibullvalene has very recently been shown by lwarnura[’5al
to be formed in the photolysis of cyclooctatetraene at
-50 “C.Our photochemical finding is paralleled by the
elegant thermal conversion of octamethylcyclooctatetraene to octamethylsemibullvalene reported by
Criegee r1Zbl.
A recent development is the findinglljC1 that benzobarrelene (59) on sensitization gives the same reaction
as barrelene. However, in the present instance, the
same product (60) can in principle arise from initial
vinyl-vinyl bridging (process a) or benzo-vinyl bridging (process b). Labeling experiments “ 5 C l show that
vinyl-vinyl bonding is preferred for the triplet. However, in unsensitized runs benzocyclooctene (61) is
formed from the singlet by a route involving initial
benzo-vinyl bonding.
8. The Occurrence of Mobius Systems in Organic
Chemistry and Use of this Concept in
One concept which has been of great utility in organic
chemistry is the Hiickel rule which specifies that for
ground state cyclic x-electron systems, 4n-I-2 electrons
afford a system with appreciable delocalization stabilization and these systems are the aromatic ones; the
4n systems are said to be “anti-aromatic”. The preceding statement is correct only when these cyclic systems
are made up of a set of atomic or hybrid orbitals in
such a way that there i s no sign inversion (or an even
number of sign inversions) 1 *J.
However, there are systems in organic chemistry which
have a single sign inversion (or an odd number of sign
inversions). In an intriguing article [161, Heilbronner
noted that it might be possible to synthesize a Mobius
molecule in which twisting of the x system along the
molecule would lead to eventual overlap of what was
[I5a] H . E. Zimmerman and H . Iwamura, J. Amer. chem. SOC.
90, 4763 (1968).
[15bl R . Criegee and R . Askani, Angew. Chem. 80, 531 (1968);
Angew. Chem. internat. Edit. 7, 537 (1968).
[15cl H . E. Zimmerman, R . S . Givens, and R . M . Pagni, J . Amer.
chem. SOC.90, 6096 (1968).
[*I The set of orbitals discussed is the arbitrary, definitional set
(i.e. the so-called “basis set”) prior to mixing to give molecular
orbitals. The sign refers to the wavefunction and is unrelated to
formal charge.
[161 E . Heilbrotmer, Tetrahedron Letters 1964, 1923.
Angew. Chem. internat. Edit.
1 Vol. 8 (1969) No.
the top portion of the x system with the bottom; this
is depicted schematically in Fig. 10. Additionally,
Heilbronner gave an algebraic formula describing the
molecular orbital energies of such a molecule.
Fig. 10. Heilbronner’s Mobius polyene concept. A : plus lobes tilting
inward. B: minus lobes tilting inward. C: sign inversion.
We suggested subsequently that it might be useful to
focus attention on the presence or absence of a sign
discontinuity in a molecule. In this we disregard the
precise geometry and concern ourselves only with
finding molecules that have such a single sign inversion
in a cyclic array of orbitals which may include s
orbitals as well as p.
The reason for this is that the secular determinant, the final
molecular orbital energies, and also the form of molecular
orbitals are not directly aware of geometry but are responsive only to the extent of overlap of such a cyclic array of
orbitals in the Huckel approximation. We can term such
systems “Mobius-like species”, whether they are ground
state or transition state molecules. Hence they are Mobiuslike more in the mathematical sense than geometrically.
One point worth repeating here is that the cyclic array of
orbitals one considers is the group of orbitals set up for
purposes of definition and called the “basis set”: this should
not be confused with groups of the same orbitals taken in
combinations to form molecular orbitals.
We find that molecules composed of a single cycle of
orbitals then fall into two categories: those of the
Huckel variety and those of the Mobius variety. The
Huckel type will always have zero or an even number
of sign inversions; the Mobius type will have one or
an odd number of sign inversions, depending on just
how the basis set of atomic orbitals is arbitrarily
The reason for considering these two types of orbital
systems is that there is a general and consistent pattern
of molecular orbitals formed by each of the two. For
the Hiickel system this is most easily seen by using
the mnemonic device of Frosr[171 in which one draws
a circle of radius 129 (see Fig. l l a ) . The polygon
with the same geometry as the cyclic array of orbitals
is inscribed with one vertex down. The center of the
circle is taken as the energy of an electron isolated in
a single orbital of the set and not allowed to distribute itself; we take this energy as our convenient but
arbitrary zero. Corresponding to the vertical displacement of each intersection of the polygon with the
circle there is a molecular orbital of that energy
which results from quantum mechanical mixing of the
individual orbitals. Frost’s mnemonic is a convenient
way of geometrically paraphrasing Hiickel’s original
[171 A . Frost and B. Musulin, J. chem. Physics 21, 572 (1953).
If the orbitals are parallel p orbitals and at normal x
bonding distances, then the value of I2P the radius
of the circle, will be twice the normal resonance integral between two p orbitals of a n system and the MO’s
given by the mnemonic are those of the organic, cyclic
systems. However, if the orbitals are those of a cyclic
transition state or of a molecule with different overlap,
the value of I p I will vary proportionally with this
The array of molecular orbitals will be the same qualitatively
but will be more compressed or expanded dependingon thesize
of the circle. When the overlap is not equal everywhere or
when some orbitals are s rather than p, then the simple
picture gives only a qualitative approximation to the MO
Now, for systems with a single sign inversion (or a n
odd number) in a single cyclic array of orbitals the
MO energies can be obtained by a mnemonic device
proposed by the present author 11*,19,19aJ which gives
exact solutions to the Heilbronner formula for Mobius
systems. The author’s device differs from the FrostHuckel mnemonic only in inscribing the polygon with
one side down in the circle. Also, the device is applicable to Mobius systems which are Mobius-like in the
sense of merely having a single sign inversion while
not geometrically resembling a Mobius system in a
simple [*I manner [ 1 8 , 1 9 , 1 9 4 . For convenience we
term such systems comprised of three orbitals in a
cyclic array as “Mobius cyclopropenyl”, those
with four orbitals as “Mobius cyclobutadiene”, etc.
These are given in Fig. 11 b. Again it must be recognized that the radius of the circle is twice the resonance
integral for adjacent orbitals of the species considered.
As noted by Heilbronner, Mobius cyclic polyenes are
twisted and fi [ will be a smaller quantity than the
usual Po In our work we have noted that the circle
radius must be adjusted for differing overlap.
1 1.
Inspection of Fig. l l a shows that the bonding MO’s
of the Huckel systems will be filled with 4 n t 2 elec-
(a )
Fig. Ila. Device by Frost for obtaining MO energies of Hiickel systems (energy units of I3
(a): Huckel cyclopropenyl. (b): Hiickel
cyclobutadiene. (c): Hiickel cyclopentadienyl. (d): Hiickel benzene.
(e): Hiickel cycloheptatrienyl.
Fig. 1 l b .
Device by Zimmerman for obtaining molecular orbital
energies of Mobius systems (energy units of B [18, 19, 19al. (a) MObius cyclopropenyl. (b): Mobius cyclobutadiene. (c): Mobius cyclopentadienyl. (d): Mobius benzene. (e): Mobius cycloheptatrienyl.
I 1).
I 1)
[18] H . E. Zimmerman, J. Amer. chem. SOC.88, 1564 (1966);
88, 1566 (1966).
(191 H. E. Zimmerman, Science (Washington) 153, 837 (1966).
[19a] H . E. Zimmerman, Photochem. and Photobiol. 7, 519
[*I However, one can consider such systems to be Mobius in the
geometric sense by considering the overlap of two adjacent
orbitals as the attachment of two adjacent strips of surface with
the plus and minus lobes of an orbital representing an upper or
lower side of the strip. +Orbitals are then considered as having
only one side, plus or minus.
trons; this is no surprise. We find, on the contrary,
that the bonding MO’s of the Mobius systems are
filled with 4n electrons, and this is interesting. For the
first excited states in the one electron approximation,
where an electron is promoted from the highest occupied to the lowest vacant MO, one finds just the
reverse. Here in excited state chemistry, it is the 4n
electron systems which have the lower electronic energy in molecules with Hiickel-like orbital overlap;
and the 4n+2 electron systems which are of lower
energy in molecules with Mobius-like overlap [IYJ.
One application of this theory to photochemistry is in
the photochemical cyclization of butadiene and hexatrienes to give cyclobutenes and cyclohexadienes,
respectively. In the case of the butadiene-cyclobutadiene reaction, overlap of the top lobes at C-1 and C-4
of butadiene leads at an intermediate stage along the
reaction coordinate to a species which is approximately isoelectronic with Huckel cyclobutadiene (i.e.
no sign inversions or an even number depending on
choice of the basis set of p orbitals); this closure has
been termed disrotatory [201. The intermediate species
is depicted in Fig. 12a. The MO’s are given by the
drawing (b) in Fig. l l a .
Alternatively, different stcreochemistry results by
overlap of the top lobe at one end of the butadiene
molecule with the bottom lobe of the other end. At
some point along the reaction coordinate one has a
cyclic array of orbitals with one (or an odd number)
of sign inversions and with overlap between the terminal orbitals not too different in degree from that
between the other adjacent orbitals. This is then a
Mobius-like system; it is depicted in Fig. 12b, and the
distribution of MO’s is given by the drawing (b) in
Fig. l l b [+I.
With the MO’s available for the two alternative
partially closed species, we may draw a correlation
diagram [211 (Fig. 13). For this one does have to know
the placement of the butadiene MO’s; however, additionally it is only necessary to connect molecular orbitals of reactant with those of the intermediate species
with the same ordering. This mode of drawing the
correlation diagram is then an alternative to the use
of symmetry [20,221.
It is seen that for the disrotatory (Huckel) closure, the
highest bonding MO becomes antibonding in the reaction while this is not true in the conrotatory (Mobius) reaction. Therefore, for a ground state reaction,
Hiickel closure will lead to a doubly excited state of
product and is said to be “forbidden” (actually in the
thermal reaction one would be considering the reverse
[20] a) R . B. Woodward and R . Hoffmann, J. Amer. chem. SOC.
87, 395 (1965); b) 87, 2511 (1965); c) R . Hoffmann and R. B.
Woodward, ibid. 87, 2046 (1965); d) 87, 4389 (1965).
[*I A minor point is that due to the twisting and lessened overlap in these species, the radius of the circle used in Figs. l l a and
l l b will be less than the usual 2 I$ol. We assume as an approximation that the amount of twisting and lessened overlap is
similar for the two species.
[21] E.g. C. A . Coulson: VaIence. Oxford University Press, London 1952, pp. 93, 100, 101.
[22] H . C. Longuet-Higgins and E. W. Abrahamson, J. Amer.
chem. SOC.87, 2046 (1965).
Angew. Chetn. internat. Edit. 1 Vol. 8 (1969)1NO. 1
process of cyclobutenes opening to butadienes). For
the photochemical process, study of the correlation
diagram in Fig. 1 3 shows that the excited state process
Fig. 12a.
Disrotatory (Hiickel-like) closure of butadiene.
Fig. 12b. Conrotatory (Mobius-like) closure of butadiene; sign inversion occurs at the site indicated by the arrow.
Fig. 15a. 1,7-Antarafacial hydrogen transfer; a Mobius system thus
favoring the 4n electron ground state process (sign change indicated by
Fig. 15b. 1,7-Suprafacial hydrogen transfer, a Huckel system favoring
the 4n electron redistribution in the excited state (no sign change).
Fig. 15c. The partially rearranged Zwitterion of the Type A rearrangement. One sign inversion and a Mobius system favored for the 4n electron redistribution process in the ground state; m, positive orbital sign.
negative orbital sign.
- 162
application to the two alternative 1,7-hydrogen migrations, suprafacial and antarafacial, as well as to the
Type A dienone transformation.
Huckei stage
Mobius stage
Fig. 13. Correlation diagrams fortwo types of butadiene closure
9. Conclusion
which is favored is the Huckel one. These conclusions
derive both from consideration of the energy of the
system at the Huckel versus the Mobius stage as well
as by consideration of the number of the antibonding
electrons in the product compared to the reactant if
no change in configuration (i.e. electron assignment)
occurs in the reaction.
A few other examples of the utility of the concept are
of interest. The hexatriene closure to cyclohexadiene
is shown in Fig. 14. Additionally, in Fig. 15 we see
0 L?
Huckel stage
Mobius stage
Fig. 14. Correlation diagrams for two types of hexatriene closure.
Angew. Chem. internat. Edit. J YoI. 8 (1969) / No. I
The preceding discussion makes it clear that photochemistry is amenable to mechanistic discussion. It
seems that many solution photochemical reactions
follow pathways dictated by energetic considerations,
tending to minimize molecular energy in the reaction
process. It appears that quite often the excited state
molecule rearrangement begins but that the excited
state of product is not formed; rather electronic excitation is lost before this geometry is reached. The
present article has summarized %ome of the recent
resclts of the author's research with an attempt to
focus attention on different types of findings and
Support of our research by N I H Grant GM07487 and
the National Science Foundation is greatly appreciated.
Received: April 16, 1968
[A 675 IE]
German version: Angew. Chem. 8I,45 (1969)
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photochemistry, mechanistic, organiz
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