Inorganic Chemistry
Article
complex in THF with MeCN. IR (KBr): ν 3049, 2958, 2902, 2863,
1601, 1584, 1549, 1450, 1424, 1337, 1277, 1203, 1143, 1000, 840, 788,
732, 697, 671, 533 cm−1. Anal. Calcd for C80H65F2Fe2N3O7·
(CH3CN)1.5·(CH2Cl2)2.8: C, 63.24; H, 4.65; N, 3.87. Found: C,
63.28; H, 4.81; N, 3.82%. mp (decomp) = 272.9 °C.
THF with pentane. IR (KBr): ν 3049, 2954, 2924, 2854, 1942, 1713,
1666, 1601, 1579, 1545, 1428, 1389, 1320, 1203, 1186, 1147, 1095,
1004, 883, 840, 788, 736, 702, 632, 542 cm−1. Anal. Calcd for
C70H44F2Fe2N2O9S·(CH2Cl2)1.5, 62.86; H, 3.47; N, 2.05; Found: C,
63.20; H, 3.53; N, 1.94%. mp (decomp) = 244.1 °C.
[Fe2(PIMIC4)(Ph3CCO2)(MeCN)] (8). In an anaerobic drybox, solid
H3PIMIC4 (75.0 mg, 0.075 mmol) and Ph3CCO2H (21.6 mg, 0.075
mmol) were dissolved in 3.0 mL of THF. A 2.0 mL solution of THF
containing [Fe2(Mes)4] (44.1 mg, 0.075 mmol) was added to the
reaction vessel, and the mixture was stirred for 1 h. The crystallization
was performed as described above for 6. The solid material was
collected by filtration and washed with pentane to give the desired
diiron complex (91.8 mg, 85%). Crystals suitable for X-ray diffraction
studies were obtained by layering a solution of the complex in THF
with MeCN. IR (KBr): ν 3056, 3031, 2918, 2850, 1578, 1545, 1490,
1444, 1418, 1378, 1322, 1304, 1284, 1200, 1175, 1152, 1097, 1085,
1036, 985, 790, 745, 699, 673, 547 cm−1. Anal. Calcd for
C85H71F2Fe2N3O7·CH3CN·CH2Cl2: C, 69.44; H, 5.03; N, 3.68.
Found: C, 69.71; H, 4.88; N, 3.54%. mp (decomp) = 286.5 °C.
[Fe2(PIMIC5)(AnthCO2)(MeCN)] (9). In an anaerobic drybox,
solid H3PIMIC5 (150.0 mg, 0.15 mmol) and AnthCO2H (33.3 mg,
0.15 mmol) were dissolved in 6.0 mL of THF. A 5 mL solution of
THF containing [Fe2(Mes)4] (88.3 mg, 0.15 mmol) was added to the
reaction vessel, and the mixture was stirred for 1 h. The crystallization
was performed as described above for 6. The solid material was
collected by filtration and washed with MeCN to give the desired
diiron complex (128.0 mg, 63%). Crystals suitable for X-ray diffraction
studies were obtained by layering a solution of the complex in either
THF or dichloromethane with MeCN. IR (KBr): ν 3049, 2958, 2902,
2863, 1601, 1579, 1553, 1445, 1428, 1320, 1277, 1203, 1147, 996, 844,
788, 732, 697, 671, 533 cm−1. Anal. Calcd for C81H67F2Fe2N3O7·
CH3CN·CH2Cl2: C, 68.63; H, 4.94; N, 3.81. Found: C, 68.84; H, 4.89;
N, 3.54%. mp (decomp) = 263.5 °C.
[Fe2(F2PIM)(Ph3CCO2)2] (15). In an anaerobic drybox, solid
H2F2PIM (51.5 mg, 0.075 mmol) and Ph3CCO2H (43.2 mg, 0.15
mmol) were dissolved in 3.0 mL of THF. A 2.0 mL solution of THF
containing [Fe2(Mes)4] (44.1 mg, 0.075 mmol) was added to the
reaction vessel, and the mixture was stirred for 1 h. The dark red
solution was evaporated to dryness, and the residue was redissolved in
toluene. The solution was filtered through a glass wool plug and
layered with pentane. Red crystals formed over several days. The solid
material was collected by filtration and washed with pentane to give
the desired diiron complex (81.0 mg, 76%). Crystals suitable for X-ray
diffraction studies were obtained with the same method. IR (KBr): ν
3053, 3027, 2927, 2854, 1950, 1878, 1804, 1597, 1588, 1553, 1448,
1376, 1329, 1203, 1186, 1147, 1000, 840, 788, 732, 699, 546 cm−1.
Anal. Calcd for C80H56F2Fe2N2O9S: C, 70.08; H, 4.12; N, 2.04. Found:
C, 69.10; H, 4.07; N, 1.95%. mp (decomp) = 176.1 °C.
[Fe2(PIMIC4)(o-Ph2PC6H4CO2)(MeCN)] (16). In an anaerobic
drybox, solid H3PIMIC4 (80.0 mg, 0.080 mmol) and o-
Ph2PC6H4CO2H (24.5 mg, 0.080 mmol) were dissolved in 3.0 mL
of THF. A 2.0 mL solution of THF containing [Fe2(Mes)4] (47.1 mg,
0.080 mmol) was added to the reaction vessel, and the mixture was
stirred for 1 h. The crystallization was performed as described above
for 6. The solid material was collected by filtration and washed with
pentane to give the desired diiron complex (78.5 mg, 67%). Crystals
suitable for X-ray diffraction studies were obtained by layering a
solution of the complex in CH2Cl2 with MeCN. IR (KBr): ν 3053,
2958, 2919, 2850, 1579, 1540, 1424, 1406, 1255, 1086, 1043, 1025,
866, 836, 797, 745, 693, 563 cm−1
. Anal. Calcd for
C84H70F2Fe2N3O7P·(CH2Cl2)0.5: C, 69.68; H, 4.91; N, 2.88. Found:
[Fe2(PIMIC6)(AnthCO2)(MeCN)] (10). In an anaerobic drybox,
solid H3PIMIC6 (154.2 mg, 0.15 mmol) and AnthCO2H (33.3 mg,
0.15 mmol) were dissolved in 6.0 mL of THF. A 5 mL solution of
THF containing [Fe2(Mes)4] (88.3 mg, 0.15 mmol) was added to the
reaction vessel, and the mixture was stirred for 1 h. The crystallization
was performed as described above for 6. The solid material was
collected by filtration and washed with MeCN to give the desired
diiron complex (181.1 mg, 89%). Crystals suitable for X-ray diffraction
studies were obtained by layering a solution of the complex in THF
with MeCN. IR (KBr): 3049, 2954, 2902, 2859, 1597, 1579, 1549,
1445, 1424, 1316, 1281, 1203, 1143, 1000, 840, 788, 732, 697, 672,
538 cm−1. Anal. Calcd for C82H69F2Fe2N3O7·CH3CN·(CH2Cl2)0.5: C,
70.07; H, 5.09; N, 3.86. Found: C, 69.93; H, 5.08; N, 3.59%. mp
(decomp) = 308.3 °C. [Fe2(PIMIC6)(AnthCO2)]·(CH2Cl2) (11) was
obtained by layering a solution of complex in toluene and CH2Cl2 with
pentane.
[Fe3(μ3-O)(HPIMIC4)2(AnthCO2)2(MeCN)] (12) and [Fe4(μ-
O)2(μ−OH)2(PIMIC4)2] (13). In an anaerobic drybox, [Fe2(PIMIC4)-
(AnthCO2)(MeCN)] (27.4 mg, 0.020 mmol) was dissolved in
anhydrous CH2Cl2. MPPH (3.3 mg, 0.020 mmol) was added to the
reaction mixture, and a dark brown solution formed immediately. The
mixture was stirred for 1 h and layered with MeCN. After 2 d, X-ray
diffraction quality crystals formed as a mixture of dark brown
rectangular blocks (12) and brown needles (13). The solid material
was collected by filtration and washed with MeCN (13.6 mg).
[Fe2(F2PIM)(AnthCO2)2(THF)] (14). In an anaerobic drybox, solid
H2F2PIM (69.0 mg, 0.10 mmol) and AnthCO2H (44.4 mg, 0.20
mmol) were dissolved in 4.0 mL of THF. A 2.0 mL solution of THF
containing [Fe2(Mes)4] (58.8 mg, 0.10 mmol) was added to the
reaction vessel, and the mixture was stirred for 1 h. The dark red
solution was evaporated to dryness, and the residue was redissolved in
CH2Cl2. The solution was filtered through a glass wool plug. The
solution was layered first with toluene then with pentane. After several
days, a large amount of red powder formed. The solid material was
collected by filtration and washed with pentane to give the desired
diiron complex (45.6 mg, 37%). Crystals suitable for X-ray diffraction
studies were obtained by layering a solution of complex in CH2Cl2 and
C, 69.56; H, 4.49; N, 2.84%. mp (decomp) = 276.1 °C.
[Fe2(PIMIC4)(o-PhSC6H4CO2)(MeCN)] (17). In an anaerobic
drybox, solid H3PIMIC4 (100.0 mg, 0.10 mmol) and o-
PhSC6H4CO2H (23.0 mg, 0.10 mmol) were dissolved in 4.0 mL of
THF. A 3.0 mL solution of THF containing [Fe2(Mes)4] (58.8 mg,
0.10 mmol) was added to the reaction vessel, and the mixture was
stirred for 1 h. The crystallization was performed as described above
for 6. The solid material was collected by filtration and washed with
pentane to give the desired diiron complex (108.0 mg, 78%). Crystals
suitable for X-ray diffraction studies were obtained by layering a
solution of the complex in CH2Cl2 with MeCN. IR (KBr): ν 3053,
2954, 2902, 2859, 1601, 1584, 1545, 1424, 1402, 1337, 1281, 1203,
1181, 1000, 840, 788, 740, 697, 672, 538 cm−1. Anal. Calcd for
C78H65F2Fe2N3O7S·CH3CN·(CH2Cl2)0.3: C, 68.66; H, 4.92; N, 3.99.
Found: C, 68.69; H, 4.77; N, 3.91%. mp (decomp) = 255.6 °C.
[Fe2(PIMIC4)(o-Ph2CHC6H4CO2)(MeCN)] (18). In an anaerobic
drybox, solid H3PIMIC4 (50.0 mg, 0.050 mmol) and o-
Ph2CHC6H4CO2H (14.4 mg, 0.050 mmol) were dissolved in 2.0
mL of THF. A 1.5 mL solution of THF containing [Fe2(Mes)4] (29.4
mg, 0.050 mmol) was added to the reaction vessel, and the mixture
was stirred for 1 h. The crystallization was performed as described
above for 6. The solid material was collected by filtration and washed
with pentane to give the desired diiron complex (46.0 mg, 64%).
Crystals suitable for X-ray diffraction studies were obtained by layering
a solution of the complex in CH2Cl2 with MeCN. IR (KBr): ν 3054,
3023, 2950, 2859, 1601, 1584, 1550, 1424, 1403, 1333, 1286, 1200,
1187, 1001, 836, 789, 750, 694, 672, 538 cm−1. Anal. Calcd for
C85H71F2Fe2N3O7·(CH3CN)3.5·(CH2Cl2)0.2: C, 71.13; H, 5.30; N,
5.85. Found: C, 71.04; H, 4.99; N, 5.87%. mp (decomp) = 304.6 °C.
ASSOCIATED CONTENT
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Inorg. Chem. XXXX, XXX, XXX−XXX