Syntheses
1.91 (6 H, s, CH3). δC(400 MHz; solvent DMSO-d6 standard
SiMe4) 170.34, 162.46 (CO); 149.43, 141.06, 132.51, 130.52,
126.61, 126.45, 125.89, 125.33 (Ar), 24.15 (Me) (observed 11
out of 12 expected signals). FT-IR/cmϪ1 (Nujol) ν 3278m,
3240m, 3285m, 3128m (NH); 1683s, 1664s, 1645s (CO). mp
270–274 ЊC. m/z 432.2 (FABϩ, TG/G ϩ DMSO matrix).
[N-(2-Aminophenyl)amino]acetamide (2). Acetic anhydride
(0.94 g, 9.2 mmol) was added dropwise to a solution of
phenylenediamine (1.0 g, 9.2 mmol) dissolved in 20 mL of dry
CH2Cl2 at 0 ЊC. The reaction mixture was stirred for 2 h at 0 ЊC
during which time a white precipitate formed. The reaction
mixture was refrigerated overnight, resulting in the formation
of a white crystalline compound that was collected by filtration.
The compound was washed with cold CH2Cl2, Et2O and dried
under vacuum to yield 2, as a white solid (0.75 g, 54%). δH(400
MHz; solvent DMSO-d6 standard SiMe4) 9.09 (1 H, s, NH),
7.15 (1 H, d, J 7.8 Hz, ArH), 6.88 (1 H, dd, J 7.8 Hz, 7.8 Hz,
ArH), 6.70 (1 H, d, J 7.8 Hz, ArH), 6.52 (1 H, dd, J 7.8 Hz, 7.8
Hz, ArH), 4.83 (2 H, s, NH2), 2.02 (3 H, s, CH3). δC(400 MHz;
solvent DMSO-d6 standard SiMe4) 169.05 (CO); 142.81,
126.59, 126.19, 124.36, 116.94, 116.63 (Ar); 24.16 (Me). FT-IR/
cmϪ1 (Nujol) ν 3455m, 3362m, 3260m (NH2); 1641s, 1587s,
2,6-Bis[N,NЈ-(2-ferrocenylamidophenyl)carbamoyl]pyridine
(H41Fc). H41Fc was synthesized by a similar procedure to that
used for H41Me using 3 (1.8 g, 5.7 mmol). The yellow–orange
H41Fc was isolated in 70% yield (1.6 g). δH(500 MHz; solvent
DMSO-d6 standard SiMe4), 11.3 (2 H, s, NH), 9.69 (2 H, s,
NH), 8.50 (2 H, d, J 7.8 Hz, pyrH), 8.38 (1 H, t, J 7.8 Hz,
pyrH), 8.00 (2 H, d, J 7.8 Hz ArH), 7.62 (2 H, d, J 7.8 Hz,
ArH), 7.45 (2 H, dd, J 7.8 Hz, 7.8 Hz, ArH), 7.39 (2 H, dd, J 7.8
Hz, 7.8 Hz, ArH), 4.68 (4 H, FcH), 4.21 (4 H, FcH), 3.94 (10 H,
FcH). δC(500 MHz; solvent DMSO-d6 standard SiMe4) 169.57,
161.13 (CO); 148.04, 141.12, 130.76, 130.29, 126.52, 126.06,
125.78, 125.47, 124.65 (Ar); 74.62, 70.94, 69.35, 68.39 (Fc).
FT-IR/cmϪ1 (Nujol) ν 1695s, 1599s, 1526s (CO). m/z 771.2
(FABϩ, NBA ϩ CH3CN matrix). E1/2 = 340 mV (vs. Agϩ/0, ∆Ep
= 111 mV, ia × icϪ1 = 1.07, CH3CN).
1535s, 1497s (CO, NH, and aromatic C᎐C). m/z 150 (Mϩ). mp
130–134 ЊC.
᎐
N-(2-Aminophenyl)aminocarbonyl]ferrocene (3). Oxalyl chlor-
ide (1.17 g, 9.22 mmol) was pipetted into a 25 mL solution of
dry CH2Cl2 containing ferrocenemonocarboxylic acid (2.12 g,
9.22 mmol) and one drop of DMF. The reaction was allowed to
stir in the dark for 5 h at 0 ЊC under N2. Volatiles were removed
under reduced pressure, and the solid was triturated with
petroleum ether (bp 35–60 ЊC). Ferrocenecarbonyl chloride
(2.04 g) was isolated after removal of solvent under reduced
pressure and was used without further isolation. A THF solu-
tion of ferrocenecarbonyl chloride (2.04 g) was then added
dropwise to a THF solution of 1,2-phenylenediamine (0.887 g,
8.21 mmol) and triethylamine (0.831 g, 8.21 mmol) at Ϫ50 ЊC.
The reaction was monitored by TLC (4 : 1 CHCl3 : EtOAc)
using the disappearance of the 1,2-phenylenediamine spot to
indicate completion of the reaction. The reaction mixture was
then filtered to remove the triethylammonium hydrochloride
salt and the filtrate dried under reduced pressure. The resulting
yellow–orange solid was dissolved in chloroform, washed with
water and extracted with 1 M HCl. The product was isolated by
precipitation by adjusting the pH > 12 with 1 M NaOH. The
resulting yellow solid was collected on a medium glass frit,
rinsed with H2O, and dried at 100 ЊC under reduced pressure to
give 3 (1.25 g, 49%). δH(400 MHz; solvent DMSO-d6 standard
SiMe4) 9.16 (1 H, s, NH), 7.08 (1 H, d, J 7.8 Hz, ArH), 6.98
(1 H, dd, J 7.8 Hz, 7.8 Hz, ArH), 6.80 (1 H, d, J 7.8 Hz, ArH),
6.63 (1 H, dd, J 7.8 Hz, 7.8 Hz, ArH), 4.97 (2 H, m, Fc), 4.81
(2 H, s, NH2), 4.43 (2 H, m, Fc), 4.24 (5 H, s, Fc). δC(400 MHz;
solvent DMSO-d6 standard SiMe4) 167.99 (CO), 143.12,
126.63, 126.29, 123.83, 116.63, 116.50 (Ar), 76.15, 70.38, 69.56,
68.67 (Fc). FT-IR/cmϪ1 (Nujol), ν 3476m, 3384m (NH2); 3271s
(NH); 1636s (CO). mp 190 ЊC (decomp.). m/z 319.2 (FABϪ,
NBA ϩ CH2Cl2 matrix).
(Et4N)2[CuH21Me(OAc)ؒCl]. H41Me (0.20 g, 0.46 mmol) was
dissolved in DMF and treated with solid KH (0.037 g, 0.92
mmol). After the gas evolution ceased, solid Cu(OAc)2 (0.084 g,
0.46 mmol) was added, which caused a color change from
yellow to green. The mixture was stirred for 2 h after which
1 equivalent of KOAc was separated by filtration. Two equiv-
alents of Et4NCl (0.15 g, 0.92 mol) were then added to the
filtrate and the mixture was allowed to stir for 2 h. The insoluble
product (KCl) was separated by filtration and the filtrate was
concentrated under reduced pressure to yield a green solid,
which was dissolved in CH3CN and kept for crystallization
by slow diffusion of diethyl ether (0.320 g, 78%). Found: C,
58.12; H, 7.47; N, 12.71. (Et4N)2[CuH21Me(OAc)ؒCl]ؒCH3CN
(C43H65Cl CuN8O6) requires C, 58.09; H, 7.37; N, 12.60%.
FT-IR/cmϪ1 (Nujol) ν 3212m, 3165m (NH); 1669s, 1625s,
1607s, 1588s (CO). λmax/nm (CH3CN) 620 (ε/mol dmϪ3 cmϪ1
230). µeff = 1.92 µB (solid, 298 K). g|| = 2.22, A|| = 178 G, g⊥ = 2.04,
A⊥ = 14 G (CH2Cl2/toluene, 77 K).
(Et4N)2[CuH21Me(Cl)ؒCl]. This compound was synthesized
following the route used for (Et4N)2[CuH21Me(OAc)(Cl)] using
CuCl2 (0.062 g, 0.46 mmol) as the metal ion precursor. The salt
was isolated as a green crystalline solid in 80% yield (0.30 g).
Found: C, 56.53; H, 7.05; N, 11.74. (Et4N)2[CuH21Me(Cl)ؒCl]
(C39H59Cl2CuN7O4) requires C, 56.82; H, 7.21; N, 11.89%.
FT-IR/cmϪ1 (Nujol) ν 3205m, 3164m (NH); 1668s, 1627s,
1607s, 1587s (CO). λmax/nm (CH3CN) 634 (ε/mol dmϪ3 cmϪ1
338). µeff = 1.90 µB (solid, 298K), g|| = 2.21, A|| = 175 G, g⊥ = 2.04
(CH2Cl2/toluene, 77 K).
(Et4N)2[CuH21Fc(OAc)ؒCl]. This compound was synthesized
by the same route as (Et4N)2[Cu(H21Me)(OAc)(Cl)] using H41Fc
(0.355 g, 0.46 mmol) and Cu(OAc)2 (0.84 g, 0.46 mmol). The
compound was purified by crystallization with CH3CN and
diethyl ether, to yield green crystals (0.320 g, 59% yield). Found:
C, 58.76; H, 6.35; N, 8.13. (Et4N)2[CuH21Fc(OAc)ؒCl]ؒCH3CN
(C59H76ClCuFe2N7O7) requires C, 58.76; H, 6.35; N, 8.12%.
FT-IR/cmϪ1 (Nujol) ν 3212m, 3165m (NH); 1669s, 1625s,
1607s, (CO). λmax/nm (CH3CN) 603 (ε/mol dmϪ3 cmϪ1 230).
µeff = 1.92 µB (solid, 298K), g|| = 2.22, A|| = 174 G, g⊥ = 2.04, A⊥ =
15 G (DMF, 77 K). E1/2 = 275 mV (vs. Agϩ/0, ∆Ep = 95 mV,
ia × icϪ1 = 1.19, CH3CN).
2,6-Bis[N,NЈ-(2-acetamidophenyl)carbamoyl]pyridine
(H41Me). Triethylamine (1.05 mL, 7.50 mmol) was added into a
solution of 2 (1.0 g, 6.7 mmol) in 50 mL of dry THF at Ϫ50 ЊC
under dinitrogen. Pyridine-2,6-dicarbonyl dichloride (0.77 g,
3.8 mmol) was dissolved in 5.0 mL of THF and added dropwise
to the above mixture. The reaction was monitored using
TLC by the disappearance of the monoacylated starting
reagent. Triethylamine hydrochloride was removed by filtration
after 2 h stirring and volatiles removed under reduced pressure.
The residue was dissolved in chloroform, washed with water,
5% NaOH, brine, and anhydrous Na2SO4. Volatiles were
removed under reduced pressure and the residue was washed
with diethyl ether to yield a white solid H41Me (1.25 g, 77%).
δH(400 MHz; solvent DMSO-d6 standard SiMe4) 10.93 (2 H, s,
NH), 9.77 (2 H, s, NH), 8.39 (2 H, m, pyH), 8.32 (1 H, m, pyH),
7.75 (2 H, m, ArH), 7.56 (2 H, m, ArH), 7.25 (4 H, m, ArH),
K[CuH21Fc(OAc)]. H41Fc (0.26 g, 0.34 mmol) in DMF
was deprotonated with KH (0.027 g, 0.68 mmol) under an
argon atmosphere. The reaction was allowed to continue until
H2 evolution ceased. Solid Cu(OAc)2 (0.061 g, 0.34 mmol) was
J. Chem. Soc., Dalton Trans., 2002, 1714–1720
1715