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Transition Met Chem (2014) 39:17–24
The reaction was cooled to room temperature, filtered and
mixture was heated to 50 °C for 12 h, cooled to RT and
concentrated in vacuo to precipitate a yellow solid, which
was isolated by vacuum filtration and washed with hex-
anes. The crude product was recrystallized from ethanol.
the filtrate was combined with
a 1:1 mixture of
CH2Cl2:H2O (100 mL). The aqueous layer was extracted
twice with CH2Cl2 and all of the organic fractions were
combined, dried over MgSO4 and filtered. The filtrate was
concentrated under reduced pressure producing a dark
brown oil, which was adsorbed on silica gel and purified
using column chromatography, [(hexanes/ethyl acetate
(2:1)], followed by recrystallization of the yellow powder
from CH2Cl2/hexanes. Yield, 0.3 g (41 %). 1H NMR
(300 MHz, CDCl3): d 8.00 (s, 1H), 7.46 (dd, 1H), 7.41 (dd,
1H), 7.26 (m, 1H), 7.19 (dd, 1H), 7.09 (m, 2H), 6.77 (s,
1H), 4.67 (s, 2H). 13C NMR (75.5 MHz, CDCl3): d 148.0,
139.5, 138.4, 137.6, 131.3, 128.7, 128.0, 127.3, 127.0,
126.9, 126.7, 126.5, 118.7, 118.1. MS (EI ?): m/z 302
(M ? , 100 %). HRMS (EI ?) Calc’d for C14H10N2S2O2:
302.01837, found: 302.01803. FT-IR (film, cm-1): 3,474
(br), 3,377 (br), 2,359 (sh), 1,620 (sh), 1,549 (sh), 1,505
(sh), 1,312 (sh), 1,263 (sh), 1,238 (sh), 1,103 (m), 843 (sh),
739 (sh), 480 (sh).
1
Yield, 0.1 g (73 %) of 10. H NMR (600 MHz, CDCl3): d
8.80 (s, 2H), 8.79 (d, 2H), 8.43 (d, 2H), 7.91 (t, 2H), 7.60
(s, 2H), 7.56 (d, 2H), 7.45 (m, 4H), 7.14 (t, 2H). 13C NMR
(151 MHz, CDCl3): d 163.7, 154.7, 149.7, 145.9, 139.7,
136.8, 128.5, 127.9, 126.9, 126.3, 125.3, 122.6, 117.8. MS
(EI ?): m/z 450 (M ? , 27 %), 372 (M-C5H4N, 100 %).
HRMS (EI ?): Calculated for C26H18N4S2: 450.09729
found: 450.09708. FT-IR (film, cm-1): 3,404 (br), 1,957
(sh), 1,624 (sh), 1,481 (sh), 1,083 (br), 895 (m), 731 (br).
[{(phen)2Fe}2(4)]4BPh4 (11)
4 (0.1 g, 0.2 mmol) was slurried into deoxygenated ethanol
(20 mL) and heated to 50 °C to produce a clear yellow
solution. Fe(phen)2Cl2 (0.3 g, 0.5 mmol) was added to the
solution resulting in a color change from bright yellow to
red with stirring continued for 16 h. At this point, an excess
of solid NaBPh4 was added and the resulting mixture was
stirred for an additional 12 h. A brown precipitate was
isolated by vacuum filtration, washed with water and die-
thyl ether. Yield, 0.4 g (65 %). MS (ESI ? , CH3CN): m/z
915 (M-4BPh4-2phen, 11 %). Anal. calc’d for
2,5-Di-(2-thienyl)-4-aminoaniline (9)
8 (0.3 g, 0.8 mmol) was combined with a mixture of eth-
anol (20 mL) and concentrated HCl (7.5 mL). The solution
was sparged with N2 for 0.5 h followed by the slow addi-
tion of mossy tin (1.5 g, 12.6 mmol). After the addition,
the reaction was stirred under N2 for 3 days. The ethanol
was removed in vacuo, and the remaining solution was
diluted into 1:1 mixture of H2O:diethyl ether (50 mL).
K2CO3 was added to the mixture until neutral, and the
solution was filtered through a bed of Celite. The filtrate
was separated and the aqueous layer was extracted twice
with diethyl ether. All of the ether fractions were com-
bined, dried over MgSO4 and filtered. Concentration in
vacuo precipitated an orange solid, which was isolated by
vacuum filtration and washed with hexanes. Yield, 0.1 g
(51 %). 1H NMR (300 MHz, CDCl3): d 7.38 (dd, 2H), 7.27
(td, 2H), 7.14 (dd, 2H), 6.84 (s, 2H), 3.72 (s, 4H). 13C NMR
(75.5 MHz, CDCl3): d 140.7, 136.2, 127.6, 126.0, 125.3,
121.5, 118.6. MS (EI ?): m/z 272 (M ? , 100 %). HRMS
(EI ?): Calc’d for C14H12N2S2: 272.04419 found:
272.04430. FT-IR (film, cm-1): 3,404 (sh), 3,227 (sh),
1,606 (sh), 1,527 (sh), 1,495 (sh), 1,441 (sh), 1,409 (sh),
1,256 (sh) 1,165 (br), 874 (sh), 845 (sh), 738 (sh).
C162H124B4Br2Fe2N12 (found) C: 76.2 (76.0), H: 4.9 (4.7),
N: 6.6 (6.9 %). FT-IR (film, cm-1): 3,443 (br), 1,634 (m),
1,144 (br), 843 (s), 739 (m). UV–Vis (CH3CN/toluene,
1:1): kmax = 512 nm (e = 3.5 9 104 M-1cm-1).
[{(phen)2Fe}2(10)]4X [X = BPh4 (12) or PF6 (13)]:
10 (0.1 g, 0.2 mmol) was dissolved in deoxygenated eth-
anol (20 mL). Fe(phen)2Cl2 (0.2 g, 0.4 mmol) was added
to the solution resulting in a color change from bright
yellow to red/orange. The mixture was stirred for 24 h
followed by the addition of excess NaBPh4 or NaPF6 with
stirring continued for 12 h. Each of the red precipitates
were isolated by vacuum filtration, washed with water and
diethyl ether. For 12: Yield, 0.4 g (84 %). MS (ESI ? ,
CH3CN): m/z 2560 (M ?). Anal. calc’d for C170H130
N12S2B4Fe2 (found %) C: 79.7 (79.7), H: 5.1 = (5.2), N:
6.6 (6.4 %). FT-IR (film, cm-1): 3,433 (br), 1,630 (br),
1,084 (w), 736 (br). UV–Vis (CH3CN/toluene, 1:1):
kmax = 515 nm (e = 3.2 9 104 M-1cm-1). For 13: Yield,
0.3 g (78 %). MS (ESI ? , acetonitrile): m/z 1717 (M-
PF6). Anal. calc’d for C74H50N12S2P4F24Fe2 (found %) C:
47.7 (47.5), H: 2.7 (2.6), N: 9.0 (9.1 %). FT-IR (film,
cm-1): 3,429 (br) 1,634 (m), 1,427 (s), 1,095 (br), 841 (s),
737 (m), 557 (s). UV–Vis (CH3CN/toluene, 1:1):
kmax = 514 nm (e = 2.7 9 104 M-1cm-1).
2,5-Di-(2-thienyl)-N,N-bis(pyridine-2-
ylmethylene)benzene-1,4-diamine (10)
9 (0.1 g, 0.4 mmol) was dissolved in ethanol (25 mL) and
to this solution was added 2-pyridinecarboxaldehyde
˚
(0.1 g, 0.9 mmol) and 4 A molecular sieves. The reaction
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