Materials
K. Tanaka and M. Haruta, J. Catal., 1998, 178, 566;
(c) M. Valden, X. Lai and D. W. Goodman, Science, 1998, 281,
1647; (d) M. Comotti, C. D. Pina, R. Matarrese and M. Rossi,
Angew. Chem., Int. Ed., 2004, 43, 5812; (e) H. Tsunoyama,
H. Sakurai, Y. Negishi and T. Tsukuda, J. Am. Chem. Soc.,
All solvents including dry CH2Cl2 were from Kanto Chemical
and were used without further purification. Iodosylbenzene
(PhIO), styrene, and poly(N-vinyl-2-pyrrolidone) (PVP-K15,
MW B10000) were purchased from TCI. The chloromanga-
nese(III) complexes of tetraphenylporphyrin [Mn(TPP)Cl] and
tetramesitylporphyrin12 [Mn(TMP)Cl] were synthesized accor-
ding to previously described procedures.13 Au55(PPh3)12Cl6
(3, denoted here as Au:PPh3) was prepared by diborane
reduction of Au(PPh3)Cl.14 Au:SC12 (1) and Au:SBn (2) were
synthesized by ligand exchange reaction of 3 with dodeca-
nethiol and benzylthiol, respectively.3 Au:PVP (4) was pre-
pared by NaBH4 reduction of HAuCl4 in the presence of PVP
according to a previously described procedure.15 All clusters
have a diameter of B1.5 nm from TEM and/or SAXS
analyses.
2005, 127, 9374; (f) A. Abad, P. Concepcio
H. Garcıa, Angew. Chem., Int. Ed., 2005, 44, 4066;
´
n, A. Corma and
´
(g) D. I. Enache, J. K. Edwards, P. Landon, B. Solsona-Espriu,
A. F. Carley, A. A. Herzing, M. Watanabe, C. J. Kiely,
D. W. Knight and G. J. Hutchings, Science, 2006, 311, 362.
3 Y. Murakami and K. Konishi, J. Am. Chem. Soc., 2007, 129,
14401.
4 K. Konishi, F. Xu and Y. Murakami, Chem. Lett., 2006, 35, 476.
5 (a) B. Meunier, Chem. Rev., 1992, 92, 1411; (b) C. L. Hill and
B. C. Schardt, J. Am. Chem. Soc., 1980, 102, 6374; (c) J. T. Groves,
W. J. Kruper and R. C. Haushalter, J. Am. Chem. Soc., 1980, 102,
6375; (d) J. P. Collman, L. Zeng and R. A. Decreau, Chem.
Commun., 2003, 2974; (e) M. L. Merlau, S. Cho, S. Sun,
S. T. Nguyen and J. T. Hupp, Inorg. Chem., 2005, 44, 5523;
(f) W. J. Song, M. S. Seo, S. D. George, T. Ohta, R. Song,
M. Kang, T. Tosha, T. Kitagawa, E. I. Solomon and W. Nam,
J. Am. Chem. Soc., 2007, 129, 1268.
6 Examples of related Mn complexes: (a) Z. Gross, G. Golublov and
L. Simkhovich, Angew. Chem., Int. Ed., 2000, 39, 4045;
(b) S. H. Wang, B. S. Mandimutsira, R. Todd, B. Ramdhanie,
J. P. Fox and D. P. Goldberg, J. Am. Chem. Soc., 2004, 126, 18.
7 (a) Colloids and Colloid Assemblies, ed. F. Caruso, Wiley-VCH,
Weinheim, 2004; (b) M. Brust, J. Fink, D. Bethell, D. J. Schiffrin
and C. Kiely, J. Chem. Soc., Chem. Commun., 1995, 1655;
R. L. Whetten, M. N. Shafigullin, J. T. Khoury, T. G. Schaaff,
I. Vezmar, M. M. Alvarez and A. Wilkinson, Acc. Chem. Res.,
1999, 32, 397; (c) A. C. Templeton, W. P. Wuelfing and
R. W. Murray, Acc. Chem. Res., 2000, 33, 27.
8 R. W. Lee, P. C. Nakagaki and T. C. Bruice, J. Am. Chem. Soc.,
1989, 111, 1368.
9 (a) J. T. Groves and M. K. Stern, J. Am. Chem. Soc., 1988, 110,
8628; (b) R. D. Arasasingham, G. X. He and T. C. Bruice, J. Am.
Chem. Soc., 1989, 115, 7985.
Oxidation reactions
Typically, solid PhIO (39.6 mg, 180 mmol) was added to a
20 ml Schlenk tube containing a dry CH2Cl2 solution of 1
(0.03 mmol in 1.8 mL) and naphthalene (B20 mg, internal
standard), and the mixture was stirred at 25 1C under argon.
After 3 h, a CH2Cl2 solution of Mn(TPP)Cl (0.18 mmol/
0.2 mL) and styrene (105 mL, 900 mmol) were successively
added. Aliquots of the reaction mixture were taken at appro-
priate intervals and subjected to GC analysis to determine the
yields of the oxidation products and were then subjected to
absorption spectroscopy after centrifugation followed by
dilution with CH2Cl2. All kinetic runs were conducted in
duplicate or triplicate to check the reproducibility.
10 R. Zhang, J. H. Horner and M. Newcomb, J. Am. Chem. Soc.,
2005, 127, 6573.
11 J. P. Collman, J. I. Brauman, P. D. Hampton, H. Tanaka,
D. S. Bohle and R. T. Hembre, J. Am. Chem. Soc., 1990, 112, 7980.
12 J. S. Lindsey and R. W. Wagner, J. Org. Chem., 1989, 54,
828.
References
13 K. Konishi. K. Oda, K. Nishida, T. Aida and S. Inoue, J. Am.
Chem. Soc., 1992, 114, 1313.
14 G. Schmid, R. Pfeil, R. Boese, F. Bandermann, S. Meyer, G. H.
M. Calis and J. W. A. van der Velden, Chem. Ber., 1981, 114, 3634.
15 H. Tsunoyama, Y. Negishi and T. Tsukuda, J. Am. Chem. Soc.,
2006, 128, 6036.
1 For recent reviews, see: (a) P. Burks, Chem. Eng. News, 2007,
September 24, 87; (b) T. Ishida and M. Haruta, Angew. Chem., Int.
Ed., 2007, 46, 7154; (c) A. S. K. Hashmi and G. J. Hutchings,
Angew. Chem., Int. Ed., 2006, 45, 7896.
2 For selected examples, see: (a) M. Haruta, T. Kobayashi, H. Sano
and N. Yamada, Chem. Lett., 1987, 16, 405; (b) T. Hayashi,
ꢀc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2008 New J. Chem., 2008, 32, 2134–2139 | 2139