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2.8. ReCl(CO)3(5,5%(4-OHCNH-3,5-i-Pr2-
C6H2ꢁCC)2-2,2%-bipy) (9)
Complex 4 (200 mg, 0.32 mmol) and HCCꢁC6H2-3,5-
i-Pr2-4-NHCHO (151 mg, 0.66 mmol) were suspended
in 40 ml of a mixture of 1:1 (v/v) triethylamine–THF.
PdCl2(PPh3)2 (36 mg, 0.05 mmol) and CuI (72 mg, 0.05
mmol) were added. The mixture was stirred at 50–60°C
for 45 h. During this time, a yellow precipitate formed
which was isolated by filtration. The yellow solid was
washed several times with ether and methylene chloride
and dried under vacuum. Yield: 220 mg, 75%. IR
(CH2Cl2, cm−1): 2178 (w, CC); 2021 (vs, CO); 1923 (s,
CO); 1902 (s, CO); 1695 (s, NHCHO). 1H-NMR
(DMSO-d6, two isomers): l 9.60 (s) and 9.53 (d, J=
11.96 Hz, minor isomer, 2H, CHO) 9.12 (d, 2H, J=
1.47 Hz, 6,6%-bipy H’s); 8.86 (d, 2H, J=9.78 Hz,
3,3%-bipy H’s); 8.51 (dd, 2H, J=8.54, J=1.95 Hz,
4,4%-bipy H’s), 8.35 (s) and 7.96 (d, J=11.47 Hz, minor
isomer, 2H, NH); 7.53 (s, minor isomer) and 7.52 (s,
4H, C6H2), 3.29–3.05 (m, 4H, CH), 1.17 (d, 2H, CH3).
13C-NMR (DMSO-d6): l 232.8, 197.1, and 190.0 (CO),
160.7 (CHO), 153.5, 146.5, 141.8, 133.2, 127.2, 126.8,
124.7, 123.1, and 120.2 (phenyl and bipyridine), 97.1
and 83.8 (CC), 28.1 (CH), 23.1 (CH3). Anal. Calc. for
C43H42O5N4ClRe: C, 56.39; H, 4.59; N, 6.12. Found: C,
56.48; H, 5.06; N, 6.02%. FAB MS (187Re): 916 [M]+;
882 [M−Cl+1]+.
2.10. ReCl(CO)3(3,8-dibromophenanthroline) (11)
This complex was obtained following the procedure
described for 10. ReCl(CO)5 (0.100 g, 0.276 mmol),
3,8-dibromophenanthroline (0.092 g, 0.276 mmol). The
complex is an orange–yellow solid (0.123 g, yield:
69.5%). IR (CH2Cl2, cm−1): 2027 (s, CO); 1927 (s, CO);
1
1905 (s, CO). H-NMR (CDCl3): l 9.42 (d, 2H, J=
2.01 Hz); 8.71 (d, 2H, J=2.00 Hz); 7.99 (s, 2H).
13C-NMR (DMSO-d6): l 196.7 and 189.1 (CO), 153.7,
144.2, 141.3, 131.1, 128.0, 120.8 (phenanthroline). Anal.
Calc. for C15H6Br2N2O3ClRe: C, 28.10; H, 0.94; N,
4.37. Found: C, 28.09; H, 1.01; N, 4.31%. FAB MS
(79Br187Re): 642 [M]+; 607 [M−Cl]+.
2.11. ReCl(CO)3(3-(4-HOCHNꢁC6H4ꢁCC)-
phenanthroline) (12)
First, 4-formamido-trimethylsilylethynylbenzene was
prepared by the reaction of 4-iodoformylaniline (5.0 g,
20.2 mmol) and trimethylsiylacetylene (3.5 ml) in the
presence of CuI (0.4 g, 2.1 mmol) and PdCl2(PPh3)2
(0.35 g, 0.5 mmol). The product is a white crystalline
1
2.9. ReCl(CO)3(3-bromophenanthroline) (10)
solid (2.97 g, yield 68%). H-NMR (CDCl3), two iso-
mers: l 8.72 (d, J=11.38 Hz) and 8.40 (d, J=1.4 Hz,
1H, CHO), 7.47 (m, 4H, C6H4), 7.13 (br) and 7.00 (d,
J=8.5 Hz, 1H, NH), 0.246 (s, 9H, CH3). IR (CH2Cl2,
cm−1): 1705 (s, NHCHO). This compound was then
treated with potassium hydroxide in THF to afford
4-formamido-ethynylbenzene as a white crystalline
ReCl(CO)5 (0.143 g, 0.395 mmol) was refluxed in
THF for 14 h (monitored by IR). After cooling to r.t.,
3-bromo-1,10-phenanthroline (0.1020 g, 0.395 mmol)
was added. The resulting mixture was stirred at r.t. for
several hours (monitored by IR). After removal of the
solvent, the solid residue was recrystallized from
methanol–dichloromethane. Yellow solid. Yield: 0.193
g, 87%. IR (CH2Cl2, cm−1): 2025 (s, CO); 1925 (s, CO);
1
solid. H-NMR (CDCl3), two isomers: l 8.73 (d) and
8.40 (s, 1H, CHO), 7.50 (m, 4H, C6H4), 7.19 (s) and
6.60 (d, 1H, NH), 3.08 (s, 1H, CCH). IR (CH2Cl2,
cm−1): 1705 (s, NHCHO).
1
1901 (s, CO). H-NMR (CDCl3): l 9.43 (d, 1H, J=1.9
Hz); 9.42 (dd, 1H, J=1.3 Hz); 8.71 (d, 1H, J=1.9 Hz);
8.57 (dd, 1H, J=8.2, J=1.4 Hz); 8.07 (d, 1H, J=8.9
Hz); 7.97 (d, 1H, J=8.9 Hz); 7.92 (dd, 1H, J=8.2,
J=5.1 Hz). 13C-NMR (DMSO-d6): l 197.3, 197.0, and
189.5 (CO), 154.6, 153.8, 145.4, 144.4, 141.2, 139.4,
131.0, 130.5, 128.9, 126.8, 126.8, and 120.5 (phenan-
throline). Anal. Calc. for C15H7BrN2O3ClRe: C, 31.90;
H, 1.25; N, 4.96. Found: C, 31.46; H, 1.26; N, 4.94%.
FAB MS (187Re): 564 [M]+; 529 [M−Cl]+.
A flask was charged with ReCl(CO)3(3-bromo-
phenanthroline) (49.6 mg, 0.0881 mmol), HCCꢁC6H4-4-
NHCHO (20.9 mg, 0.144 mmol), PdCl2(PPh3)2 (6.3 mg,