(
)
344
R. Jin et al.rJournal of Molecular Catalysis A: Chemical 116 1997 343–347
.
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benzene manganese IV tetraphenylporphyrin
complexes. We report here the isolation and
characterization of another two monomeric
was vigorously stirred for 50 s. The resulting
red–brown solution was quickly cooled to
y308C and filtered. After the filtrate was poured
into hexane cooled to y308C, the precipitate
was filtered. The red–brown oxidation product
was recrystallized three times from CH2Cl2r
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mono iodosylbenzene tetraphenylporphinato -
manganese IV derivatives 2a and 2b,
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y
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.
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LMn IV TPP OIPh Ls4-MeOC6H4O and
4-t-BuC6H4Oy and the oxidation activity of
hexane cooled to y308C giving 0.045 g 35%
.
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these complexes for cyclohexane and styrene.
yield of pure product 2a. It was found that: C,
67.31; H, 3.63; N, 5.03; Mn, 5.48; I, 12.57%.
Values calculated for C57H40N4MnIO3 were:
C, 67.73; H, 3.99; N, 5.54; Mn, 5.44; I, 12.55%.
The complex 2b was similarly isolated. To a
2. Experimental
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2.1. General
solution of 100 mg 0.096 mmol of the com-
plex 1b, which was prepared from the
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Commercially available organic and inor-
ganic compounds were used without further pu-
rification except for the solvent, which was
distilled by known methods before use.
ClMn III TPP and sodium 4-t-butylphenolate by
a similar method as was prepared 1a. To 25 ml
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of dichloromethane was added 500 mg 2.30
.
mmol of iodosylbenzene. The mixture was vig-
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Chloro tetraphenylporphinato manganese III
orously stirred for 45 s. The subsequent proce-
dure was similar to the method for preparation
of complex 2a. The pure product 2b was ob-
tained in 50% yield. It was found that: C, 68.28;
H, 3.91; N, 5.06; Mn, 5.62; I, 12.17%. Values
calculated for C60H46N4MnIO were: C, 68.45;
H, 4.40; N, 5.32; Mn, 5.22; I, 12.05%.
w x
was prepared by the known method 9 . Visible
spectra were determined on a UV-3000 spectro-
photometer. Infrared spectra were obtained by a
FTS-20 infrared spectrophotometer. X-band
ESR spectra were determined as a solid at room
temperature using a JES-FE3AS ESR spectrom-
eter.
2.3. Oxidation of cyclohexane or styrene by 2
( )
(
) (
2.2. Synthesis of LMn IV TPP OIPh Ls4-
MeOC6 H4Oy or 4-t-BuC6 H4Oy
)
To the mixture of 6 ml of dichloromethane
and 2 ml of cyclohexane or 0.5 ml of styrene
degassed by N2 was added about 0.02 mmol of
high-valent manganese complexes 2. The mix-
ture was stirred for 1 h under N2 at room
temperature. After the reaction mixture was
passed through a short silica gel column to
remove the reduced complex, the product was
analysed by GLC.
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To a solution of 1.0 g 1.4 mmol of
ClMn III TPP in 100 ml of ethyl alcohol was
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added a solution of 6.0 g 51.7 mmol of sodium
4-methoxyphenolate in water. The reaction sys-
tem was degassed with nitrogen for 1 h and then
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6.0 g 158.7 mmol of sodium borohydride was
added to the mixture. The mixture was stirred
for 2 h under nitrogen atmosphere. The result-
ing solution was distilled to remove the alcohol,
filtered, rinsed with 500 ml of hot water and
3. Results and discussion
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dried in vacuo. Crude 4-MeOC6H4O Mn III -
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TPP 1a was purified by recrystallization from
The formation of the monomeric mono-
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dichloromethanerpetroleum ether. To a solution
iodosylbenzene manganese IV tetraphenylpor-
phyrin complexes was affected by the axial
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of 100 mg 0.099 mmol of the complex 1a in
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25 ml of dichloromethane was added 500 mg
ligand of tetraphenylporphinato manganese III
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derivatives, LMn III TPP. It was reported that
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2.30 mmol of iodosylbenzene and the mixture
Jin, Rizhen
