OAT from (Oxo)managanese(V) Corroles to Sulfides
A R T I C L E S
3-Mn(O): MS (ES+) (%). 999.69 [M]+ (100), 1024.75 [M +
Na]+. UV-vis (EtOAc) λmax[nm] (relative %): 349(100), 409(85),
518(20). 1H NMR (CDCl3): δ ) 9.4 (d, J ) 4.6 Hz, 2H), 9.01 (d,
J ) 4.5 Hz, 2H), 8.84(overlapping of two doublets, 4H), 8.1 (d, J
1-Mn: C41H16F15MnN4O2, M ) 936.52, monoclinic, space group
P21/c, a ) 14.816(3) Å, b ) 39.268(8) Å, c ) 7.422(1) Å, ꢀ )
104.29(3)°, V ) 4184.5(13) Å3, Z ) 4, T ) 180(2) K, Dc ) 1.487
g/cm3, µ(Mo KR) ) 0.422 mm-1, 7086 unique reflections to θmax
) 25.00°, 568 refined parameters, R1 ) 0.096 for 5515 observations
with I > 2σ(I), wR2 ) 0.280 for all unique data. (this structure
determination is characterized by relatively low precision due to
poor-quality crystals and the obtained diffraction data).
1a-Mn: C41H8Br8F15MnN4O2, M ) 1567.73, monoclinic, space
group P21/c, a ) 23.2370(10) Å, b ) 7.4218(4) Å, c ) 32.1102(16)
Å, ꢀ ) 104.732(2)°, V ) 5274.6(4) Å3, Z ) 4, T ) 110(2) K, Dc
) 1.974 g/cm3, µ(Mo KR) ) 6.401 mm-1, 9433 unique reflections
to θmax ) 25.30°, 642 refined parameters, R1 ) 0.054 for 5291
observations with I > 2σ(I), wR2 ) 0.136 for all unique data.
3-Mn: C41H22Br4F5MnN4O2, M ) 1072.21, orthorhombic, space
group P212121, a ) 11.7695(2) Å, b ) 16.4116(3) Å, c )
19.4712(2) Å, V ) 3760.99(3) Å3, Z ) 4, T ) 110(2) K, Dc )
1.894 g/cm3, µ(Mo KR) ) 0.719 mm-1, 8859 unique reflections to
θmax ) 27.88°, 516 refined parameters, R1 ) 0.033 for 7658
observations with I > 2σ(I), wR2 ) 0.075 for all unique data.
5-Mn: C45H33Cl6MnN4O4, M ) 961.39, orthorhombic, space
group Pbcn, a ) 38.806(8) Å, b ) 15.342(3) Å, c ) 14.647(3) Å,
V ) 8720(3) Å3, Z ) 8, T ) 293(2) K, Dc ) 1.465 g/cm3, µ(Mo
KR) ) 0.719 mm-1, 7608 unique reflections to θmax ) 25.02°, 529
refined parameters, R1 ) 0.062 for 4214 observations with I > 2σ(I),
wR2 ) 0.187 for all unique data.
) 8.4 Hz, 2H), 8.0 (d, J ) 8.3 Hz, 2H), 7.6(t, J ) 8.4 Hz, 2H): 19
F
NMR (CDCl3): δ ) -132.0 (d, J ) 23.4 Hz, 1F), -132.5 (d, J )
23.4 Hz, 1F), -147.4 (t, J ) 22.0 Hz, 1F), 156.3 (t, J ) 20.8 Hz,
1F), -156.7 (t, J ) 22.0 Hz, 1F).
4-Mn(O): MS (ES+) (%). 702.82 [M + H]+ (50), 685.83 [M -
O]+ (20), 726.85 [M + Na]+ (100). UV-vis (EtOAc) λmax[nm]
(relative %): 347(100), 405(79), 518(18).). 1H NMR (CDCl3): δ )
9.41 (d, J ) 4.4 Hz, 2H), 9.18 (d, J ) 4.3 Hz, 2H), 8.99 (d, J )
4.8 Hz, 2H), 8.93 (d, J ) 4.7 Hz, 2H), 7.45-7.82 (m, 9H). 19F
NMR (CDCl3): δ ) -104.3 (br s, 2F), -104.8 (br s, 1F), -105.09
(br s, 2F), -105.4(br s, 2F).
5-Mn(O): MS (ES+) (%). 799.84 [M]+ (100), 824.89 [M + Na]+
(50). UV-vis (EtOAc) λmax [nm] (relative %): 347(100), 405(83),
518(19). 1H NMR (CDCl3): δ ) 9.36 (d, J ) 4.5 Hz, 2H), 9.01 (d,
J ) 4.4 Hz, 2H), 8.77 (d, J ) 4.8 Hz, 2H), 8.73 (d, J ) 4.7 Hz,
2H), 7.89 (d, J ) 7.7 Hz, 4H), 7.85 (d, J ) 8.1 Hz, 2H) 7.76-7.89
(m, 9H).
1a-Mn(O): UV-vis (CH2Cl2) λmax[nm] (relative %): 388(100),
421(83), 537(23). 19F NMR (CDCl3): δ ) -132.3 (two ovelaping
doublets, 3F), -132.6 (two ovelaping doublets, 3F), 146.1 (t, J )
20.7 Hz, 2F), -146.2 (t, J ) 20.7 Hz, 1F), -157.7 (m, 6F).
2a-Mn(O). UV-vis (CH2Cl2) λmax[nm] (relative %): 373(85),
5a-Mn: C41H8Br8Cl6MnN4O2, M ) 1504.51, monoclinic, space
group P21/n, a ) 11.1966(2) Å, b ) 18.4159(3) Å, c ) 24.8914(6)
Å, ꢀ ) 99.9206(6)°, V ) 5055.75(17) Å3, Z ) 4, T ) 110(2) K,
Dc ) 1.977 g/cm3, µ(Mo KR) ) 6.940 mm-1, 11956 unique
reflections to θmax ) 27.85°, 561 refined parameters, R1 ) 0.045
for 8794 observations with I > 2σ(I), wR2 ) 0.109 for all unique
data.
1
416(100), 534(100). H NMR (CDCl3): δ ) 7.9 (d, J ) 7.8 Hz,
1H), 7.6 (d, J ) 7.7 Hz, 1H), 7.3 (dd, J ) 7.5 Hz, 2H), 7.6 (d, J
) 7.3 Hz, 1H), 4.1 (s, 3H)): 19F NMR (CDCl3): δ ) -132.5 (d, J
) 23.1 Hz, 2F), -132.8 (d, J ) 23.1 Hz, 2F), -146.7 (t, J ) 20.8
Hz, 2F), -157.9 (m, 4F).
3a-Mn(O): MS (ES+) (%). 1632.33 [M + H]+ (25), 1656.33
[M - O + CH3CN]+ (80), 1670.35 [M + CH3CN]+ (60), 1706.36
[M - O + Br]+ (100). UV-vis (CH2Cl2) λmax[nm] (relative %):
[5-Mn]*: C44H25Cl6MnN4OS, M ) 925.38, monoclinic, space
group P21/c, a ) 12.6988(2) Å, b ) 13.4937(2) Å, c ) 22.5901(5)
Å, ꢀ )95.0013(7)°, V ) 3856.16(12) Å3, Z ) 4, T ) 110(2) K, Dc
) 1.594 g/cm3, µ(Mo KR) ) 0.856 mm-1, 7875 unique reflections
to θmax ) 26.37°, 525 refined parameters, R1 ) 0.055 for 4502
observations with I > 2σ(I), wR2 ) 0.168 for all unique data.
2.8. Kinetic Experiments. Kinetic experiments were carried out
on an Agilent 8453 diode array spectrophotometer for the nonbro-
minated manganese corroles 1-Mn(O) to 5-Mn(O). The measure-
ments were performed in ethyl acetate as solvents and monitored
by UV-vis spectroscopy. The (oxo)manganese(V) corroles were
prepared by ozone oxidation of (corrolato)manganese(III) [14.7 µM
in 200 mL of ethyl acetate] solutions. For each measurement, the
(oxo)manganese(V) complex was freshly generated. The kinetic
measurements were repeated three times for each concentration,
and several wavelengths were measured. The wavelengths that differ
the most between (corrolato)manganese(III) and (oxo)manganese(V)
are 347, 482-490, and 600 nm. The substrate solutions were
prepared by dissolving thioanisole derivative in ethyl acetate. The
substrate concentrations taken for each measurement are presented
in the Table S1 (Supporting Information). GC analysis of reaction
mixtures confirmed the formation of the corresponding sulfoxides.
Reactions performed with 1a-Mn(O) to 5a-Mn(O) were much
too fast to be measured by conventional mixing. Hence, their
reactions with thioanisoles were examined by the stopped-flow
technique. One syringe contained substrate in dichloromethane, and
the other contained a solution of (oxo)manganese(V) corroles in
dichloromethane. Equal volumes were injected into the stopped-
flow cell. The constant temperature (20 °C) was assured by the
instrument configuration: water from a thermostatted bath over the
flow path and the firing syringes filled with reagents.
1
392(97), 425(100), 537(20). H NMR (CDCl3): δ ) 7.9 (d, J )
8.3 Hz, 2H), 7.3 (d, J ) 8.3 Hz, 2H), 7.5(t, J ) 8.3 Hz, 2H): 19F
NMR (CDCl3): δ ) -131.8 (d, J ) 23.6 Hz, 1F), -132.6 (d, J )
22.7 Hz, 1F), -147.4 (t, J ) 21.9 Hz, 1F), 157.6 (m, 2F).
4a-Mn(O): UV-vis (CH2Cl2) λmax[nm] (relative %): 391(100),
423(100), 537(30). 1H NMR (CDCl3): δ ) 7.53-766 (m, 9H): 19
F
NMR (CDCl3): δ ) -104.9 (br s, 1F), -105.1 (br s, 2F), -105.2
(br s, 2F), -105.5(br s, 1F).
5a-Mn(O). MS (ES+) (%). 1431.29 [M]+ (40), 1456.34 [M - O
+ CH3CN]+ (100), 1484.61 [M - O - Br]+ (50). UV-vis (CH2Cl2)
λ
max[nm] (relative %): 387(97), 422(100), 537(19). 1H NMR
(CDCl3): δ ) 7.69-7.73 (m, 9H).
2.6. Crystallography. X-ray quality crystals of 2 were grown
in hexane at low temperature (-4 °C) and 5 in a 1/1 mixture of
dichloromethane/hexane at room temperature. For all manga-
nese(III) corroles, 1-Mn, 1a-Mn, 3-Mn, 5-Mn, and 5a-Mn, single
crystals of X-ray quality were grown in ethylacetate/hexane mixtures
at room temperature. [5-Mn]* was obtained by growing crystals
in the presence of phenylmethylsulfoxide. Methods of crystal
mounting and data analysis are identical to those of previous
reports.11g
2.7. Crystal Data: 2. C38H17F10N4O, M ) 735.56, triclinic, space
j
group P1, a ) 15.0003(3) Å, b ) 16.0686(2) Å, c ) 16.5517(3)
Å, R ) 67.4337(6)°, ꢀ ) 64.9752(6)°, γ ) 75.281(6)°, V )
3406.59(10) Å3, Z ) 4, T ) 110(2) K, Dc ) 1.436 g/cm3, µ(MoKR)
) 0.126 mm-1, 15948 unique reflections to θmax ) 27.84°, 957
refined parameters, R1 ) 0.058 for 8352 observations with I > 2σ(I),
wR2 ) 0.162 for all data.
5: C37H20F6N4, M ) 634.57, monoclinic, space group P21/c, a
) 17.911(4) Å, b ) 12.858(3) Å, c ) 13.559(3) Å, ꢀ ) 110.68(3)°,
V ) 2921.4(11) Å3, Z ) 4, T ) 293(2) K, Dc ) 1.443 g/cm3, µ(Mo
KR) ) 0.113 mm-1, 5309 unique reflections to θmax ) 25.32°, 433
refined parameters, R1 ) 0.057 for 2785 observations with I > 2σ(I),
wR2 ) 0.162 for all unique data.
Determination of the Reaction Constants for the Reactions
of (Oxo)manganese(V) Corroles with Thioanisoles. The oxygen
transfer reactions were followed by UV-vis spectroscopy by
examining changes in absorbance by time. The reactions were
performed in ethyl acetate at 20 °C. The concentrations of
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J. AM. CHEM. SOC. VOL. 132, NO. 43, 2010 15237