IV
absorption of the reduced SiW11
V
form in the 500–520 nm
10 A. Messerschmidt, Multi-Copper Oxidases, World Scientific, Sin-
gapore, 1997.
range. A similar approach was not attainable in the case of
III
SiW Mn , because the SiW Mn form absorbs below 360
II
11 (a) J. Yoon, L. M. Mirica, T. D. P. Stack and E. I. Solomon, J.
Am. Chem. Soc., 2005, 127, 13680–13693; (b) E. I. Solomon, R. K.
Szilagyi, S. DeBeer George and L. Basumallick, Chem. Rev.,
2004, 104, 419–458; (c) E. I. Solomon, P. Chen, M. Metz, S.-K.
Lee and A. E. Palmer, Angew. Chem., Int. Ed., 2001, 40,
1
1
11
5
c
nm, in a region covered by absorption bands of the substrate.
IV
The contributions from the absorption of SiW V at 350 nm
1
1
ꢀ
ꢀ
1
ꢀ1
ꢀ1
V
(
e = 295 M cm ), from the absorption of SiW V at 500
1 II
nm (e = 3 M cm ), and from the absorption of SiW11Mn
at 490 nm (e = 20 M cm ) have been considered during
experimental data treatments. For the kinetic isotope effect
1
1
4
570–4590.
1
1
2 M. Sadakane and E. Steckhan, J. Mol. Catal. A: Chem., 1996, 114,
221–228.
3 (a) R. A. Marcus and H. Eyring, Annu. Rev. Phys. Chem., 1964, 15,
ꢀ1
ꢀ1
1
55–196; (b) L. Eberson, Electron Transfer Reactions in Organic
2 2
determination with SiW11V, H O was substituted with D O,
Compounds, Springer Verlag, Berlin, 1987, ch. III.
4 C. J. Schlesener, C. Amatore and J. K. Kochi, J. Am. Chem. Soc.,
1984, 106, 3567–3572.
and p-MeO-phenol was used as the substrate at 25 1C, under
otherwise identical experimental conditions as reported above.
1
1
1
5 H. Gillier-Pandraud, Bull. Soc. Chim. Fr., 1967, 1988–1995.
6 I. J. Rhile, T. F. Markle, H. Nagao, A. G. DiPasquale, O. P. Lam,
M. A. Lockwood, K. Rotter and J. M. Mayer, J. Am. Chem. Soc.,
Acknowledgements
2
17 (a) L. Eberson and M. Nilsson, Acta Chem. Scand., 1990,
006, 128, 6075–6088.
We thank the Italian MIUR for COFIN and FIRB grants,
and the University of Roma ‘La Sapienza’ for financial
support. A. S. Nunes Pontes thanks the EU for a ‘Leonardo
da Vinci’ mobility fellowship (PT/05/A/F/PL-126149).
4
4, 1062–1070; (b) L. Eberson, New J. Chem., 1992, 16,
51–156.
1
8 A. M. Khenkin, D. Kumar, S. Shaik and R. Neumann, J. Am.
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˚
din, S. Styring, B. Akermark, L. Sun and L. Hammar-
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9 (a) M. Sjo
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