Communications
1
6
16 18
18
16
O : O O: O O = 9:42:49 from the applied isotopic ratio
[8] Y.Naruta, M.Sasayama, T.Sasaki,
964; Angew. Chem. Int. Ed. Engl. 1994, 33, 1839.
9] K.Ichihara, Y.Naruta, Chem. Lett. 1998, 185.
[10] a) J.T.Groves, J.Lee, S.S.Marla, J. Am. Chem. Soc. 1997, 119,
269; b) N.Jin, J.T.Gloves, J. Am. Chem. Soc. 1999, 121, 2923.
Angew. Chem. 1994, 106,
2
2
1
6
18
1
of O: O = 3:7 in water and hydroxide anion).These results
indicated quantitative incorporation of oxygen atoms from
H O and OH into the evolved O .On the other hand, no O
evolution was detected on the controlled experiment with a
[
À
2
2
2
6
[
11] N. Jin, J.L. Bourassa, S.C. Tizio, J.T. Groves,
Angew. Chem.
IV
2
V
Mn
species 3.It was reported that H OÀMn =O can
2
2000, 112, 4007; Angew. Chem. Int. Ed. 2000, 39, 3849.
[
11]
oxidize halide anion through an oxo-transfer reaction.
Indeed, upon protonation, 2 quantitatively oxidized Cl into
ClO by an attack of the Mn =O moiety on Cl , whereas
without protonation, Cl oxidation could not be observed.
[12] a) T .J .Collins, R .D .Powell, C.Slebodnick, E .S .Uffelman,
J.
À
Am. Chem. Soc. 1990, 112, 899; b) F.M. MacDonnell, N.L.P.
À
V
À
Fackler, C.Stern, T.V.O ’Halloran, J. Am. Chem. Soc. 1994, 116,
7431; c) C.G.Miller, S.W. Gordon-Wylie, C.P. Horwitz, S.A.
Strazisar, D.K. Periano, G.R. Clark, S.T. Weintraub, T.J.
Collins, J. Am. Chem. Soc. 1998, 120, 11540; d) Z.Gross, G.
Golubkov, L.Simkhovich, Angew. Chem. 2000, 112, 4211;
Angew. Chem. Int. Ed. 2000, 39, 4045; e) B.S. Mandimutsira,
B.Ramdhanie, R .C .Todd, H .L .Wang, A A. .Zareba, R .S .
À
Thus, the protonation on 2 could form a transient intermedi-
V
ate, such as (H OÀMn =O) .The O ÀO bond formation would
2
2
V
occur by the attack of the H OÀMn =O group on water, or by
2
V
a coupling reaction between the oxo groups of each Mn =O
Czemuszewicz, D.P. Goldberg, J. Am. Chem. Soc. 2002, 124,
unit.Furthermore, as decomposition of the Mn complex was
not detected in the stoichiometric reaction presented herein,
the interconversion between 1 and 2 can be extended to a
catalytic cycle.
1
5170.
13] Y.Naruta, M.Sasayama, K.Ichihara, J. Mol. Catal. A 1997, 117,
15.
14] a) J.T.Groves, M.K.Stern, J. Am. Chem. Soc. 1988, 110, 8628;
b) Y.Oliver Su, M.K.Stern, K.A.Macor, D.Kim, J.T.Groves,
T.G.Spiro, J. Am. Chem. Soc. 1988, 110, 4158.
[
[
1
V
In conclusion, we have characterized the Mn =O por-
phyrin dimer as a key intermediate of the O evolution in
detail.The reaction of the Mn
under strong basic conditions gave the stable diamagnetic
Mn 2 intermediate 2, which has oxo and hydroxo axial ligands
derived from water and/or hydroxide ions.Addition of a small
excess amount of acid to 2 rapidly afforded a Mn species,
2
III
2
complex 1 with mCPBA
[15] J.A.Smegal, C.L.Hill, J. Am. Chem. Soc. 1983, 105, 3515.
[
16] Since the metal complexes of DTMP ligand have a long metal-
metal distance (> 6 ꢀ) and a rigid framework against inward
bending, the Mn cernters cannot be bridged by a coordinated
oxo or hydroxo anion, see Y.Shimazaki, H.Takesue, T.Chishiro,
F.Tani, Y.Naruta, Chem. Lett. 2001, 538.
V
III
2
and dioxygen was evolved quantitatively.Further studies on
the mechanism of this oxygen evolution catalyzed by the
dimanganese tetraarylporphyrin dimer are in progress in our
laboratory.
[
17] J.Bernadou, B.Meunier, Chem. Commun. 1998, 2167.
Received: August 4, 2003 [Z52564]
Keywords: manganese · O ligands · oxidation · oxygen ·
.
porphyrinoids
[
1] a) W.Ruettinger, G.C.Dismukes, Chem. Rev. 1997, 97, 1; b) R.
Manchanda, G.W.Brudvig, R.H.Crabtree, Coord. Chem. Rev.
1
995, 144, 1; c) T.J. Meyer, Acc. Chem. Res. 1989, 22, 163;
d) A.J.Bard, M.A.Fox, Acc. Chem. Res. 1995, 28, 141.
2] V.L.Pecoraro, M.J.Baldwin, A.Gelasco, Chem. Rev. 1994, 94,
07.
[
8
[
3] M.Yagi, M.Kaneko, Chem. Rev. 2001, 101, 21.
[
4] a) G.C.Dismukes, Y.Siderer, Proc. Natl. Acad. Sci. USA 1981,
66, 706; b) G.C.Dismukes, K.Ferris, P.Watnick, Photobiochem.
Photobiophys. 1982, 3, 243.
[
5] a) A.Zouni, H.T.Witt, J.Kern, P.Fromme, N.Krab, W.Saenger,
P.Orth, Nature 2001, 409, 739; b) N.Kamiya, J -. R.Shen, Proc.
Natl. Acad. Sci. USA 2003, 100, 98.
[
6] a) C.W.Hoganson, G.T.Babcock, Science 1997, 277, 1953; b) J.
Messinger, M.Badger, T.Wydrzynski, Proc. Natl. Acad. Sci.
USA 1995, 92, 3209; c) V.L. Pecoraro, M.J. Baldwin, M.T.
Caudle, W.Hsieh, N.A.Law, Pure Appl. Chem. 1998, 70, 925;
d) M .L .Gilchrist, J .A .Ball, D .W .Randall, R .D .Britt,
Proc.
Natl. Acad. Sci. USA 1995, 92, 9545; e) P.E.M.Siegbahn, R.H.
Crabtree, J. Am. Chem. Soc. 1999, 121, 117.
[
7] a) J.Limburg, J.S.Vrettos, L.M.Liable-Sands, A.L.Rheingold,
R.H.Crabtree, G.W.Brudvig, Science, 1999, 283, 1524; b) W.
Ruettinger, M.Yagi, K.Wolf, G.C.Dismukes, J. Am. Chem. Soc.
2
000, 122, 10353; c) J.Limburg, J.S.Vrettos, H.Y.Chen, J.C.
de Paula, R.H.Crabtree, G, W, Brudvig, J. Am. Chem. Soc.
001, 123, 423.
2
1
00
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2004, 43, 98 –100