phenylporphyrin. This porphyrin was metalated with FeCl3 and then
washed with 2 M hydrochloric acid, according to the usual procedure.14
Elemental analysis: H; 4.19 (4.27), C; 67.80 (68.55), N; 9.07 (9.65),
where values in parentheses are calc. for C58H43N7OFeCl3. UV-Vis;
λmax = 380 (7.00 × 104), 419 (1.84 × 105), 512 (1.73 × 104), 585 (3650),
649 (3170), 692 (3170), where λmax is in nm and values in parentheses
are molar extinction coefficients (molϪ1 l dmϪ1). 1H NMR for metal-free
mvep-TPP; δ 10.65 (1H, NH), 9.56 (2H, 4,4Ј-bpy), 9.30 (2H), 8.83
(12H, pyrrole and 4,4Ј-bpy), 8.21 (8H, o,oЈ-Ph), 8.02 (2H, mЈ-Ph), 7.84
(9H, m,p-Ph), 5.13 (2H, -CO-CH2-), 4.45 (3H, 4,4Ј-bpy), 3.45 (2H,
-CH2-4,4Ј-bpy), Ϫ2.93 (2H, pyrolle NH).
4 (a) R. Krueger and L. M. Siegel, Biochemistry, 1982, 27, 2905;
(b) J. F. Cline, P. A. Janick, L. M. Siegel and B. M. Hoffman,
Biochemistry, 1986, 25, 4647; (c) J. A. Christner, P. A. Janick, L. M.
Siegel and E. Munck, J. Biol. Chem., 1983, 258, 11157; (d) J. A.
Christner, E. Munck, T. A. Kent, P. A. Janick, J.-C. Salerno and
L. M. Siegel, J. Am. Chem. Soc., 1984, 106, 6786; (e) J. F. Madden,
S. Han, L. M. Siegel and T. G. Spiro, Biochemistry, 1989, 28, 5471;
( f ) D. E. McRee, D. C. Richardson, J. S. Richardson and L. M.
Siegel, J. Biol. Chem., 1986, 261, 10277.
5 (a) J. Tan and J. A. Cowan, Biochemistry, 1991, 30, 8910; (b) S. M.
Lui, A. Soriano and J. A. Cowan, J. Am. Chem. Soc., 1993, 115,
10483; (c) S. M. Lui and J. A. Cowan, Biochemistry, 1994, 33, 11209;
(d) S. M. Lui, W. Liang, S. Soriano and J. A. Cowan, J. Am. Chem.
Soc., 1994, 116, 4531.
6 (a) J. Ostrowski, J. Y. Wu, D. C. Rueger, B. E. Miller, L. M. Siegel
and N. M. Kredich, J. Biol. Chem., 1989, 264, 15726; (b) D. E.
McRee, D. C. Richardson, J. S. Richardson and L. M. Siegel, J. Biol.
Chem., 1986, 261, 10277.
7 K. Tsuji, M. Imaizumi, A. Ohyoshi, I. Mochida, H. Fujitsu and
K. Takeshita, Inorg. Chem., 1982, 21, 721.
8 (a) M. H. Barley, K. J. Takeuchi, W. R. Murphy and T. J. Meyer,
J. Chem. Soc., Chem. Commun., 1985, 507; (b) M. H. Barley, K. J.
Takeuchi and T. J. Meyer, J. Am. Chem. Soc., 1986, 108, 5876;
(c) M. R. Rhodes, M. H. Barley and T. J. Meyer, Inorg. Chem.,
1991, 30, 629.
§ If a carboxyl group was connected to the porphyrin ring, the intro-
duction of a viologen unit through the amide linkage failed. The NH2
group should be connected to the porphyrin ring to utilize the amide
group for the bridging linkage.
¶ ESR spectral measurements suggest that both iron porphyrin and
viologen moieties are two-electron reduced in THF–MeOH (9:1 v/v);
g = ca. 6.0 for 1 without NaBH4 and 2.32 and 1.95 for 1 with NaBH4. In
diglyme–MeOH (9:1 v/v), these ESR spectra were not observed, while
only a very small signal was observed at g = 2.02. This very small signal
suggests that the iron porphyrin moiety is one-electron reduced and
most of the viologen moieties are two-electron reduced but some
amount of the viologen is one-electron reduced in this solvent. Thus, the
number of electrons that 1 can use for the reduction reaction is less than
4. Since six electrons are necessary for the reduction of nitrobenzene to
aniline, one molecule of 1 and 2 cannot reduce nitrobenzene to aniline.
|| First, the reaction solution was thoroughly degassed through five
cycles of freeze–pump–thaw. Then, the appropriate amount of oxygen-
saturated methanol was added to the solution (ESI).
9 T. Nagata, K. Fujimori, T. Yoshimura, N. Furukawa and S. Oae,
J. Chem. Soc., Perkin Trans. 1, 1989, 1431.
10 K. S. Suslick and R. A. Watson, Inorg. Chem., 1991, 30, 912.
11 S. Sakaki, T. Kimura, T. Ogata, H. Hasuo and T. Arai, New J.
Chem., 1994, 18, 231.
12 K. Gunther, Coord. Chem. Rev., 1998, 171, 61.
1 For instance, (a) J. L. Lee, J. A. Hunt and J. T. Groves, J. Am. Chem.
Soc., 1999, 120, 6053 and 7493.
2 (a) B. H. Huynh, L. Kang, D. V. Der Vartanian, H. D. Peck and
J. LeGall, J. Biol. Chem., 1984, 259, 15373; (b) I. Moura, A. R. Lina,
J. J. G. Moura, A. V. Xavier, G. Fauque, H. D. Peck and J. LeGall,
J. Biochem. Biophys. Res. Commun., 1986, 141, 1032.
13 (a) J. S. Lindsey and R. M. Wagner, J. Org. Chem., 1989, 54, 828;
(b) L. R. Milgrom, J. Chem. Soc., Perkin Trans. 1, 1983, 2535.
14 A. D. Adler, F. R. Longo, F. Kampas and J. Kim, J. Inorg. Nucl.
Chem., 1970, 32, 2443.
15 I. Okura, Coord. Chem. Rev., 1985, 86, 53.
3 (a) J. M. Vega and H. Kamin, J. Biol. Chem., 1977, 252, 896; (b) J. R.
Lancaster, J. M. Vega, H. Kamin, N. R. Orme-Johnson, W. H.
Orme-Johnson, R. J. Krueger and L. M. Siegel, J. Biol. Chem., 1979,
254, 1268; (c) M. J. Murphy, L. M. Siegel, S. R. Tove and H. Kamin,
Proc. Natl. Acad. Sci. USA, 1974, 71, 612; (d) B. A. Crowe, P. Owen
and R. Cammack, Eur. J. Biochem., 1983, 137, 185.
Communication b000146p
J. Chem. Soc., Dalton Trans., 2000, 1015–1017
1017