Resonance Raman of Reduced 1,4-Benzoquinone
J. Phys. Chem. A, Vol. 101, No. 4, 1997 631
be significantly altered in solution. For instance, the ν9a
(4) Ding, H.; Moser, C. C.; Robertson, D. E.; Tokito, M. K.; Daldal,
F.; Dutton, P. L. Biochemistry 1995, 34, 15979.
(5) Breton, J.; Boullais, C.; Berger, G.; Mioskowski, C.; Nabedryk, E.
Biochemistry 1995, 34, 11606.
-1
frequency is higher by 19 cm in H2O than that in MeCN (1143
-
1
Vs 1162 cm in Figure 3), a fact which is most reasonably
•
-
attributed to interactions of the four hydrogen atoms of BQ
(
(
(
6) Becker, E. D. J. Phys. Chem. 1991, 95, 2818.
7) Yamakita, Y.; Tasumi, M. J. Phys. Chem. 1995, 99, 8524.
8) Zhao, X.; Imahori, H.; Sakata, Y.; Zhan, C.-G.; Kitagawa, T. Chem.
•
-
with solvents. The solvation of BQ may make the amount
of charges (positive or negative) localized at all atoms larger
than those in the gas phase.
Phys. Lett., in press.
According to the picture of the hydrogen bonding of the
(9) Tripathi, G. N. R. In AdVances in Spectroscopy; Clark, R. J. H.,
Hester, R. E., Eds.; John Wiley & Sons: New York, 1989; pp 157-218.
benzene ring with small molecules in the gas phase,4
4-50
water
(
(
(
10) Rossetti, R.; Brus, L. E. J. Am. Chem. Soc. 1986, 108, 4718.
11) Beck, S. E.; Brus, L. E. J. Am. Chem. Soc. 1982, 104, 4789.
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molecules are located at the upper part of the quinone plane.
Thus, the repulsive interaction between the protons of water
molecules and C1 or C4 may make the disposition of the CdO
group slightly out of the molecular plane. When this molecule
is deformed from the planar structure, the Raman intensity would
become weaker. If the intensity of ν8a (CdC stretch) is regarded
as standard, the intensities of ν1, ν7a, and ν9a (relative to that of
ν8a) can be used to evaluate the approximate out-of-plane
distortion of the quinone ring (C-C single bonds), C-O, and
C-H groups, respectively. The relative intensities of these
modes in water (3.8, 0.26, and 0.69, respectively) are appreciably
smaller than those in MeCN (22.2, 0.61, and 1.1, respectively),
suggesting larger nonplanar distortion in water than in MeCN,
presumably owing to the cluster formation in water. According
1
982, 2, 573.
(
(
13) Terazima, M.; Hamaguchi, H. J. Phys. Chem. 1995, 99, 7891.
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56, 51.
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19) Chang, H. M.; Jaffe, H.; Masmanidis, C. A. J. Phys. Chem. 1975,
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9, 1118.
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(
1995, 14, 503.
51
•-
to the X-ray crystallographic structure, UQ0 (UQ0: ubiqui-
none) definitely adopts nonplanar structures, and the discussion
mentioned above predicts that the relative intensities of the ν1
(21) Morrison, L. E.; Schelhorn, J. E.; Cotton, T. M.; Bering, C. L.;
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Trumpower, B. L., Ed.; Academic: New York, 1982.
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•
-
and ν7a bands (to ν8a band) are smaller than those of BQ in
MeCN. It was, in fact, as expected.52
1871.
Conclusions
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Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M.
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Stewart, J. J. P.; Pople, J. A. Gaussian 92, Pittsburgh, 1992.
Electrochemical RR spectroscopy of isotope-labeled BQ’s
combined with ab initio MO calculations has provided us with
a clear description of the electronic structures, molecular
structures, and bond properties of various reduced species of
BQ. A few marker bands, which can characterize the strength
of the CdO bonds and the nature of the six-membered ring,
were pointed out for the first time. The ν7a frequency, the
separation between ν8a and ν8b, and the appearance of a Fermi
doublet owing to ν1 and 2ν16a all indicate that a quinoid ring
gradually changes to a benzenoid ring upon reduction from BQ
(26) Zhan, C.-G.; Iwata, S. To be published.
(27) Swallow, A. J. In Functions of Quinones in Energy ConVerting
Systems; Trumpower, B. L., Ed.; Academic: New York, 1982.
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(32) Sakurai, T. Acta Crystallogr. 1968, B24, 403.
•
•-
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2-
(33) Das, M. R.; Fraenkel, G. K. J. Chem. Phys. 1965, 42, 403.
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to BQH , BQ , BQH , BQ , and BQH2. The CdO stretching
2
-
frequency suggests that the extra negative charges of BQ are
highly localized at two oxygen atoms and the RR spectra of
(35) Dollish, F. R.; Fateley, W. G.; Bentley, F. F. Characteristic Raman
Frequencies of Organic Compounds; John Wiley & Sons: New York, 1974.
2-
-
•-
BQ and BQH are alike, while an extra charge of BQ is
delocalized. These data would serve as basic information for
analyzing the RR spectra of quinones observed for biological
systems.
(36) Gu, Y.; Champion, P. M. Chem. Phys. Lett. 1990, 171, 254.
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4A, 749.
4
(
(
(
(
(
(
39) Adams, G. E.; Michael, B. D. Trans. Faraday Soc. 1967, 63, 1171.
40) Wilson, R. L. Chem. Commun. 1971, 1249.
41) Rao, P. S.; Hayon, E. J. J. Phys. Chem. 1973, 77, 2274.
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Acknowledgment. We thank Drs. Kiyoshi Tsuge, Hiroshi
Nakajima, and Prof. Koji Tanaka of this institute for their help
in electrochemical experiments and Drs. Y. Mizutani and T.
Ogura of this laboratory for their help in measurements of the
UV RR spectra. X. Z. thanks the Japanese Society for
Promotion of Science for a postdoctoral fellowship. This study
was supported by Grants-in-Aid for Scientific Research in
Priority Areas (Molecular Biometallics) from the Ministry of
Education, Science, Culture, and Sports, Japan, to T. K.
W. A., III; Blake, G. A. Science 1992, 257, 942.
(45) Rodham, D. A.; Suzuki, S.; Suenram, R. D.; Lovas, F. J.; Dasgupta,
S.; Goddard, W. A., III; Blake, G. A. Nature 1993, 362, 735.
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J. Am. Chem. Soc. 1986, 108, 1064.
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(08249106).
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References and Notes
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1) The Chemistry of Quinonoid Compounds; Patai, S., Ed.; John Wiley
Sons: New York, 1974. Functions of Quinones in Energy ConVerting
Systems; Trumpower, B. L., Ed.; Academic: New York, 1982.
(50) Atwood, J. L.; Hamada, F.; William orr, K. D. R.; Vincent, R. L.
Nature 1991, 349, 683.
(51) Silverman, J.; Stam-Thole, I.; Stam, C. H. Acta Crystallogr. 1971
B27, 1846.
(52) Zhao, X.; Kitagawa, T. To be submitted.
&
(
(
2) Okamura, M. Y.; Feher, G. Annu. ReV. Biochem. 1992, 61, 881.
3) Klinman, J. P.; David, M. Annu. ReV. Biochem. 1994, 63, 299.