Organometallics
ARTICLE
The mixture was poured into a solution of ice-cold H2O (approximately
30 mL) and filtered, and the organic layer was collected. The solution
was concentrated in vacuo, and the product 9 isolated as a yellow,
crystalline material using silica column chromatography (1:5 ethyl
acetate/hexane). Yield: 0.49 g, 82%. Mp: 81-82 °C. IR (cm-1): 1805
(s, CdO), 1266, 1069 (s, C-F). NMR: 1H (CDCl3), δ 4.69 (s, 5H, C5H5),
4.85 (t, J = 1.6 Hz, 2H, C5H4 meta), 5.17 (t, J = 1.6 Hz, 2H, C5H4 ortho);
13C (CDCl3), δ 70.23 (s, C(COF)), 72.64 (s, C5H4 meta), 72.82
(s, C5H5), 74.60 (s, C5H4 ortho), 159.91 (s, COF). Anal. Calcd for
C11H9FORu: C 47.7, H 3.27. Found: C 47.7, H 2.86.
[Ru(η5-C5H5)(η5-C5H4CO2CH2C5H5O5C2(CH3)4)] (14). Compound
9 (0.07 g, 2.53 ꢀ 10-4 mol), 1,2:3,4-di-O-isopropylidene-D-galactopyr-
anose (0.05 g, 5.20 ꢀ 10-4 mol), and DMAP (0.06 g, 5.20 ꢀ 10-4 mol)
were dissolved in DCM (10 mL) and stirred for 16 h at room
temperature. The solvent was removed in vacuo to yield an oily, yellow
residue, which was purified using silica column chromatography (3:7
ethyl acetate/hexane) to afford compound 17 as a colorless powder.
Yield: 0.07 g, 51%. Mp: 112-114 °C. IR (cm-1): 1721 (s, CdO), 1291,
1222 (s, C-O). ESMS (m/z): þve ion, calcd m/z for [M þ Na]þ 540.6,
found 541.0; NMR: 1H (CDCl3), δ 1.35, 1.36, 1.48, 1.55 (s, 12H, CH3),
3.99-4.69 (m, 6H, CH, CH2), 4.63 (s, 5H, C5H5), 4.71 (m, 2H, C5H4
meta), 5.16 (m, 2H, C5H4 ortho), 5.57 (m, 1H, OCHO); 13C (CDCl3),
δ 24.79, 25.23, 26.25, 26.39 (s, CH3), 63.21, 66.16, 70.68, 70.93, 71.30,
75.38, 96.54, 108.92, 109.76 (s, O2C(CH3)2, C(CO2CH2C5O5C2(CH3)4),
CH2, CH), 71.88, 73.05 (s, C5H4), 72.10 (s, C5H5), 170.32 (s, CO2).
Anal. Calcd for C23H28O7Ru: C 53.4, H 5.46. Found: C 54.8, H 5.81.
[Ru(η5-C5H4CO2CH2C5H5O5C2(CH3)4)2] (15). Compound 10 (0.07
g, 2.17 ꢀ 10-4 mol), 1,2:3,4-di-O-isopropylidene-D-galactopyranose
(0.05 g, 5.20 ꢀ 10-4 mol), and DMAP (0.06 g, 5.20 ꢀ 10-4 mol) were
dissolved in DCM (10 mL) and stirred for 16 h at room temperature.
The solvent was removed in vacuo to yield an oily, yellow residue, which
was purified using silica column chromatography (3:7 ethyl acetate/
hexane) to afford compound 18 as a colorless powder. Yield: 0.08 g,
45%. Mp: 159-160 °C. IR (cm-1): 1721 (s, CdO), 1292, 1272 (s, C-
O). ESMS (m/z): þve ion, calcd m/z for [M þ Na]þ 826.9, found
826.8. NMR: 1H (CDCl3), δ 1.35, 1.36, 1.48, 1.56 (s, 24H, CH3), 3.99-
4.69 (m, 12H, CH, CH2), 4.79 (m, 4H, C5H4 meta), 5.21 (m, 2H, C5H4
ortho), 5.57 (m, 2H, OCHO); 13C (CDCl3), δ 24.79, 25.27, 26.25, 26.39
(s, CH3), 63.43, 66.13, 70.68, 70.90, 71.23, 76.87, 96.50, 108.92, 109.76
(s, O2C(CH3)2, C(CO2CH2C5O5C2(CH3)4), CH2, CH), 73.34, 75.09
(s, C5H4), 169.34 (s, CO2). Anal. Calcd for C36H46O14Ru: C 53.8, H
5.77. Found: C 54.0, H 5.86.
[Ru(η5-C5H4COF)2] (10). Compound 10 was prepared by a similar
method to that described for 9, using 2 (0.38 g, 1.08 ꢀ 10-3 mol) as a
starting material. Compound 10 was isolated as a yellow, crystalline mate-
rial using silica column chromatography (1:5 ethyl acetate/hexane).
Yield: 0.25 g, 73%. Mp: 196-197 °C. IR (cm-1): 1806 (s, CdO), 1268,
1069 (s, C-F). NMR: 1H (d6-DMSO), δ 5.26 (t, J = 2.0 Hz, 4H, C5H4
meta), 5.40 (t, J = 2.0 Hz, 4H, C5H4 ortho); 13C (d6-DMSO), δ 72.56 (s,
C(COF)), 74.71 (s, C5H4 meta), 76.89 (s, C5H4 ortho), 160.85 (s,
COF). Anal. Calcd for C12H8F2O2Ru: C 44.6, H 2.50. Found: C 46.9, H
2.86.
[Ru(η5-C5H5)(η5-C5H4CO]2O (11). Compound 1 (0.03 g, 1.08 ꢀ
10-4 mol) and compound 9 (0.03 g, 1.08 ꢀ 10-4 mol) were stirred in a
solution of pyridine (5 mL) and THF (5 mL) for a period of 30 min. The
solution was cooled to 0 °C in an ice bath prior to the dropwise addition
of concentrated HCl (0.5 mL). The product was extracted from solution
with diethyl ether (10 mL), and the organic phase was washed three
times with water (10 mL) and once with a saturated solution of sodium
bicarbonate (10 mL). The organic phase was retained, dried over
anhydrous sodium sulfate, filtered, and concentrated in vacuo to yield
a pale yellow solid. Compound 11 was then isolated as a yellow powder
using silica column chromatography (1:5 ethyl acetate/hexane). Yield:
0.03 g, 22%. Mp: 150-152 °C (dec). IR (cm-1): 1713 (s, CdO), 1243
(s, C-O). ESMS (m/z): þve ion, calcd m/z for [M þ Na]þ 555.5,
found 556.4, calcd m/z for [2 M þ Na]þ 1088.1, found 1088.5. NMR:
1H (CDCl3), δ 4.70 (s, 10H, C5H5), 4.83 (m, 4H, C5H4 meta), 5.18 (m,
4H, C5H4 ortho); 13C (CDCl3), δ 70.28 (s, C(CO2)), 72.60 (s, C5H4-
meta), 74.15 (s, C5H4-ortho), 74.24 (s, C5H5), 165.78 (s, CO2). Anal.
Calcd for C22H18O3Ru2: C 49.6, H 3.41. Found: C 50.6, H 3.71.
[Ru(η5-C5H5)(η5-C5H4CO2C6H5)] (12). Compound 9 (0.07 g, 2.60 ꢀ
10-4 mol), phenol (0.05 g, 5.20 ꢀ 10-4 mol), and DMAP (0.06 g,
5.20 ꢀ 10-4 mol) were dissolved in DCM (10 mL) and stirred for 16 h
at room temperature. The solvent was removed in vacuo to yield an oily,
yellow residue, which was purified using silica column chromatography
(3:7 ethyl acetate/hexane) to afford compound 12 as a yellow solid.
Yield: 0.05 g, 55%. Mp: 96-97 °C. IR (cm-1): 1735 (s, CdO), 1269 (s,
C-O). ESMS (m/z): þve ion, calcd m/z for [M þ Na]þ 374.4, found
375.3. NMR: 1H (CDCl3), δ 4.69 (s, 5H, C5H5), 4.81 (m, 2H, C5H4
meta), 5.30 (m, 2H, C5H4 ortho), 6.99-7.49 (m, 5H, C6H5); 13C
(CDCl3), δ 70.24, 72.21, 73.59, 74.94 (s, C5H4, C5H5), 121.74, 125.71,
129.53, 151.02 (s, C6H5), 168.97 (s, CO2). Anal. Calcd for
C17H14O2Ru: C 58.1, H 4.02. Found: C 59.2, H 4.27.
[Ru(η5-C5H5)(η5-C5H4COS(CH2)2CH3)] (16). Compound 9 (0.07 g,
2.53 ꢀ 10-4 mol), n-thiopropanol (0.04 mL, 5.20 ꢀ 10-4 mol), and
DMAP (0.06 g, 5.20 ꢀ 10-4 mol) were dissolved in DCM (10 mL) and
stirred for 16 h at room temperature. The solvent was removed in vacuo
to yield an oily, yellow residue, which was purified using silica column
chromatography (3:7 ethyl acetate/hexane) to afford compound 19 as a
colorless powder. Yield: 0.04 g, 57%. IR (cm-1): 1656 (s, CdO), 1237
(s, C-S). ESMS (m/z): þve ion, calcd m/z for [2 M þ Li]þ 673.8,
found 673.9. NMR: 1H (CDCl3), δ 0.99 (t, J = 7.4 Hz, 3H, CH3), 1.63
(m, 2H, CH2CH3), 2.92 (t, J = 7.4 Hz, 2H, SCH2), 4.59 (s, 5H, C5H5),
4.75 (m, 2H, C5H4 meta), 5.20 (m, 2H, C5H4 ortho); 13C (CDCl3), δ
13.61 (s, CH3), 23.52 (s, CH2CH3), 30.55 (s, SCH2), 70.46, 72.83, 73.16
(s, C5H4, C5H5), 84.63 (s, C(COS(CH2)2CH3)), 192.65 (s, COS).
Anal. Calcd for C14H16OSRu: C 50.4, H 4.85. Found: C 51.4, H 5.08.
[Ru(η5-C5H5)(η5-C5H4CO2(CH2)2NHBoc)] (17). Compound 9 (0.07
g, 2.60 ꢀ 10-4 mol), N-Boc-ethanolamine (0.08 mL, 4.96 ꢀ 10-4 mol),
and DMAP (0.06 g, 5.20 ꢀ 10-4 mol) were dissolved in DCM (10 mL)
and stirred for 16 h at room temperature. The solvent was removed in
vacuo to yield an oily, yellow residue, which was purified using silica
column chromatography (1:1 ethyl acetate/hexane) to afford com-
pound 14 as a colorless powder. Yield: 0.07 g, 68%. Mp: 176-177 °C. IR
(cm-1): 3351 (m, N-H stretch), 1700, 1712 (s, CdO), 1536 (m, N-
H bend), 1291, 1260 (m, C-O). ESMS (m/z): þve ion, calcd m/z for
[Ru(η5-C5H4CO2C6H5)2] (13). Compound 10 (0.07 g, 2.23 ꢀ 10-4
mol), phenol (0.04 g, 4.46 ꢀ 10-4 mol), and DMAP (0.05 g, 4.46 ꢀ 10-4
mol) were dissolved in DCM (10 mL) and stirred for 16 h at room
temperature. The solvent was removed in vacuo to yield an oily, yellow
residue, which was purified using silica column chromatography (3:7
ethyl acetate/hexane) to afford compound 13 as a yellow, crystalline
material. Yield: 0.03 g, 31%. Mp: 154-156 °C. IR (cm-1): 1729 (s,
CdO), 1270 (s, C-O). ESMS (m/z): þve ion, calcd m/z for [M þ
1
[M þ Na]þ 441.5, found 441.4. NMR: H (CDCl3), δ 1.66 (s, 9H,
CH3), 3.43 (m, 2H, CH2NHBoc), 4.21 (t, J = 5.0 Hz, 2H, OCH2), 4.60
(s, 5H, C5H5), 4.73 (m, 2H, C5H4 meta), 5.15 (m, 2H, C5H4 ortho); 13
C
(CDCl3), δ 28.65 (s, CH3), 40.12 (s, CH2NH), 63.32 (s, OCH2), 71.88,
72.06, 73.19, (s, C5H4, C5H5), 79.89 (s, C(CO2(CH2)2NHBoc)),
155.86 (s, NHCO2), 170.50 (s, C5H4CO2). Anal. Calcd for
C18H23NO4Ru: C 51.7, H 5.54, N 3.35. Found: C 51.9, H 5.75, N 3.27.
[Ru(η5-C5H4CO2(CH2)2NHBoc)2] (18). Compound 10 (0.09 g, 2.69
ꢀ 10-4 mol), N-Boc-ethanolamine (0.08 mL, 4.96 ꢀ 10-4 mol), and
1
Na]þ 494.5, found 494.3. NMR: H (CDCl3), δ 4.91 (m, 4H, C5H4
meta), 5.41 (m, 4H, C5H4 ortho), 6.99-7.39 (m, 10H, C6H5); 13C
(CDCl3), δ 74.18, 75.05 (s, C5H4), 76.91 (s, C(CO2C6H5)), 121.92,
125.82, 129.46, 150.77 (s, C6H5), 167.85 (s, CO2). Anal. Calcd for
C24H18O4Ru: C 61.1, H 3.85. Found: C 61.4, H 4.58.
1401
dx.doi.org/10.1021/om100928s |Organometallics 2011, 30, 1395–1403