Job/Unit: I20555
/KAP1
Date: 08-08-12 16:38:30
Pages: 6
T. Tano, H. Sugimoto, N. Fujieda, S. Itoh
SHORT COMMUNICATION
Supporting Information (see footnote on the first page of this arti-
cle): Experimental details including physical measurements, prod-
uct analysis, and synthetic procedures.
product selectivity is significantly improved by the addition
of copper.[13] In this reaction, the primary product is methyl
hydroperoxide (MeOOH), which is produced by the direct
reaction of methane with a generated dinuclear iron active
oxygen species.[13] Our present study suggests that the role
of copper in the methane oxidation reaction of Hutchings
is the enhancement of O–O bond heterolysis of the primary
product MeOOH to give MeOH as the major product.
Mechanistic details of the O–O bond cleavage process and
application to catalytic oxidation reactions are now under
investigation.
Acknowledgments
This work was supported by a Grant-in-Aid for Scientific Research
on Innovative Areas “Molecular Activation Directed toward
Straightforward Synthesis” from the Ministry of Education, Cul-
ture, Sports, Science and Technology, Japan (SI, No. 22105007). T.
Tano acknowledges the financial support from the Global COE
program “the Global Education and Research Center for Bio-Envi-
ronmental Chemistry of Osaka University” from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
Experimental Section
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Materials: The reagents and solvents used in this study, except p-
substituted cumene hydroperoxide derivatives (XCmOOH), were
commercial products of the highest available purity that were fur-
ther purified by standard methods if necessary.[14] Ligands La [N,N-
di(2-pyridylmethyl)benzylamine] and Lb [N,N,NЈ,NЈ-tetra(2-pyr-
idylmethyl)-m-xylylenediamine] and the copper(I) complex of La,
[CuI(La)(CH3CN)](PF6) (1a), were prepared according to reported
procedures.[11,15] Cumene hydroperoxide (HCmOOH) and 8-hydro-
peroxy-p-cymene (MeCmOOH) were prepared by reported pro-
cedures.[16] Other cumene hydroperoxide derivatives, RCmOOH (R
= Et, Br, F, and NO2), were prepared in a similar manner, as de-
scribed in the Supporting Information.
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[CuI2(Lb)(CH3CN)2](PF6)2 (1b): Ligand Lb (30 mg, 60 mmol) was
treated with 2 equiv. of [CuI(CH3CN)4](PF6) (45 mg, 120 mmol) in
CH2Cl2 (1 mL) under a N2 atmosphere in a glove box (Miwa MFG
Co., Ltd. DB0–1KP). After stirring the mixture for 30 min at room
temperature, the insoluble material was removed by filtration. Ad-
dition of ether (30 mL) to the filtrate gave a pale yellow powder
that was precipitated by letting the mixture stand for 10 min. The
supernatant was then removed by decantation, and the remaining
pale yellow solid was washed with diethyl ether three times and
dried to give complex 1b in 67%. Single crystals of 1b were ob-
tained by vapor diffusion of diethyl ether into an acetonitrile solu-
–
tion of the complex. FTIR (KBr):
C36H38Cu2F12N8P2
ν
˜
=
843 cm–1 (PF6 ).
(999.8)
[CuI2(Lb)(CH3CN)2] (PF6)2: C 43.25, H 3.83, N 11.21; found C
43.31, H 4.04, N 11.45.
[CuII2(Lb)(μ-OMe)2](PF6)2(Et2O) (3bЈ): An acetonitrile solution
(1.0 mL) of 1b (12 mg, 12 mmol) was prepared in a glove box at
room temperature. The solution was cooled to –40 °C, and an ace-
tonitrile solution (100 mL) of HCmOOH (240 mm) was added by
using a microsyringe through the rubber septum cap. After stirring
the mixture for 10 min, an excess amount of precooled ether was
poured into the solution to give a blue powder that was precipitated
by letting the mixture stand for several minutes. The supernatant
was removed by filtration to give 3bЈ as a blue powder in 81%
yield. Single crystals of 3bЈ were obtained by vapor diffusion of
diethyl ether into CH3CN/MeOH (v/v = 1:1) solution of the com-
plex. FTIR (KBr): ν = 842 cm–1 (PF6 ). C38H48Cu2F12N6O3P2
–
˜
(1053.9) [CuII2(Lb)(μ-OMe)2](PF6)2(Et2O): C 42.31, H 4.59, N 7.97;
found C 42.02, H 4.61, N 8.05.
CCDC-883133 (for 1b) and -883134 (for 3bЈ) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
4
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