Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Dinuclear and Mononuclear Manganese(IV)-Radical Complexes and
Their Catalytic Catecholase Activity
Soumen Mukherjee, Thomas Weyhermüller, Eberhard Bothe, Karl Wieghardt
and Phalguni Chaudhuri*
Supplementary Materials
Spectroscopic Data:
H2L5 (R = -CH3): m.p. 139 oC. 1H NMR (500 MHz, CD2Cl2):  1.274 (s, 9H), 1.448 (s,
9H), 2.211 (s, 6H), 6.303 (s, 2H), 6.500 (s, 2H), 7.046, 7.050 (d, 1H), 7.221, 7.226 (d,
1H). 13C NMR (125 MHz, CDCl3):  21.493, 29.676, 31.722, 34.666, 35.266, 53.370,
53.586, 53.801, 54.019, 54.235, 113.373, 121.846, 121.996, 122.084, 128.714,
135.486, 139.397, 142.514, 147.238, 149.731. EI-MS: m/z (relative intensity %):
327(3.1), 326(23.7), 325(100.0), 324(3.2), 310(28.7), 121(6.3). Calculated formula
weight 325.49. Anal. calcd for C22H31NO: C, 81.18; H, 9.60; N, 4.30. Found: C, 80.0;
H, 9.6; N, 4.4.
H2L6 (R = -Cl): m.p. 175 oC, IR(KBr, cm-1): 3424s, 3327s, 2961s, 1575s, 1483s,
1222s, 1108s, 1095m, 991s, 830s, 770s, 670m. 1H NMR (CDCl3):  1.26 (s, 9H),
1.42 (s, 9H), 5.08 (s, 1H), 6.06 (s, 1H), 6.52 (m, 2H), 6.81 (b, 1H), 6.96 (b, 1H), 7.24
(s, 1H). 13C NMR (CDCl3):  29.47, 31.51, 34.34, 35.02, 113.33, 119.71, 121.45,
122.89, 126.04, 135.66, 135.92, 142.72, 148.74, 149.05.
13C
NMR (CH3OH):  30.11,
32.02, 35.17, 36.04, 113.58, 118.25, 122.16, 122.48, 128.81, 136.35, 137.75,
143.22, 150.34, 151.29. EI-MS: m/z (relative intensity %): 369(12), 368(15), 367(67),
366(24), 365(100), 354(8), 353(10), 352(45), 351(15), 350(70), 57(45), 41(14), 29(7).
Calculated formula weight 366.33. Anal. calcd for c20H25Cl2NO: C, 65.57; H, 6.88; N,
3.82. Found: C, 65.0; H, 6.9; N, 3.7.
H2L7 (R = -OCH3): m.p. 132 oC. IR(KBr, cm-1): 3413s, 3320s, 3000m, 2960s, 1602s,
1207s, 1147s, 1070m, 1059m, 823m. 1H NMR (CDCl3):  1.24 (s, 9H), 1.41 (s, 9H),
3.70 (s, 6H), 5.01 (s, 1H), 5.83 (b, 2H), 5.98 (b, 1H), 7.02 (b, 1H), 7.18 (b, 1H).
13C
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
NMR (CDCl3):  29.47, 31.55, 34.32, 34.95, 55.17, 92.08, 93.81, 121.57, 122.02,
127.26, 135.36, 142.16, 148.74, 149.13, 161.72.
13C
NMR (CH3OH):  30.13, 32.06,
35.15, 35.93, 55.50, 92.39, 94.54, 121.34, 121.73, 130.43, 136.95, 142.86, 149.83,
150.59, 163.0. EI-MS: m/z (relative intensity %) 358(31), 357(100), 342(30), 57(5).
Calculated formula weight 357.50. Anal. calcd for C22H31NO3: C, 73.91; H, 8.74; N,
3.92. Found: C, 74.1; H, 8.9; N, 4.1.
Complex 4: Anal. calcd for C66H69F18N3O3Mn: C, 58.76; H, 5.16; N, 3.12; Mn, 4.07.
Found: c, 58.8; H, 5.1; N, 3.0; Mn, 5.0. ESI(pos.)-MS (CH2Cl2): m/z 1349 [MnL43]+.
Complex 5: Anal. calcd for C66H87N3O3Mn: C, 77.31; H, 8.55; N, 4.10; Mn, 5.36.
Found: C, 77.3; H, 8.70; N, 4.0; Mn, 5.3. ESI(pos.)-MS (CH2Cl2): m/z 1025 [MnL53]+.
Magnetic measurements: eff, B (T, K) = 1.30(2), 1.70(10), 1.72(100), 1.71(200),
1.75(290). Fit parameters: J = -400 cm-1, g1=g3=2.00, g2=1.99.
Complex 6: Anal. calcd for C60H69Cl6N3O3Mn: C, 62.78; H, 6.06; N, 3.66; Mn, 4.79.
Found: C, 62.4; H, 6.1; N, 3.5; Mn, 4.9. ESI(pos.)-MS (CH2Cl2): m/z 1147 [MnL63]+.
Magnetic measurements: eff, B (T, K) = 1.09(2), 1.82(10), 1.83(100), 1.85(200),
1.88(290). Fit parameters: J = -295 cm-1, g1=g3=2.00, g2=2.05.
Complex 7: Anal. calcd for C66H87N3O9Mn: C, 70.69; H, 7.82; N, 3.75; Mn, 4.90.
Found: C, 68.9; H, 7.9; N, 3.6; Mn, 5.0. ESI(pos.)-MS (CH2Cl2): m/z 1121 [MnL73]+.
Magnetic measurements: eff, B (T, K) = 1.45(2), 1.71(10), 1.73(100), 1.73(200),
1.79(200). Fit parameters: J = -330 cm-1, g1=g3=2.00, g2=1.99.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Supplementary Material
Figure 10. X-band EPR spectra at 10 K (a) complex 1 in CH2Cl2. Conditions:
frequency 9.6359 GHz; power 400 W; modulation amplitude 10 G;
(b) complex 1 after the reaction with 2 equivalents of 3,5-DTBC in a
glove box. Conditions: frequency 9.4565 GHz; power 50.4 W;
modulation amplitude 10 G.
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Supplementary Material for Dalton Transactions
This journal is © The Royal Society of Chemistry 2004
Supplementary Material
Figure 11. Electronic spectra of the eluted solutions at different time intervals for
the aerial oxidation of DTBP to TTBD by using complex 1 as
catalyst.