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R. Wilberger et al. / Inorganic Chemistry Communications 6 (2003) 845–851
3. Synthesis
3.86%. Calc. for C14H20N2O8Re2 (716.74 g/mol): C,
23.46%; H, 2.81%; N, 3.91%. MS (DEI) m=z (%):
716.2 (83) [Mþ], 688.2 (100) [Mþ–CO], 660.2 (42) [Mþ–2
CO], 632.2 (36) [Mþ–3 CO], 604.3 (70) [Mþ–4 CO],
576.3 (24) [Mþ–5 CO], 548.2 (8) [Mþ–6 CO], 516.2 (12),
473.2 (12), 359.2 (21) [Mþ/2+H], 329.2 (44), 301.2 (11),
272.2 (10).
3.1. General procedure for 3a–f
Complex 1 and one equivalent of the amino alcohol
2a–f were dissolved in 10 cm3 octane and refluxed for 2
h. The solvent was then evaporated and the colorless
residue was washed with pentane (10 cm3) and dried in
vacuum.
3.1.3. trans-Bis½5-tert-butyl-1,1,1-tricarbonyl-azað5Þ-l-
oxað2Þ-rhenað1Þ-cyclopentane ð3cÞ
3.1.1. trans-Bis½1,1,1-tricarbonyl-5-methyl-azað5Þ-l-oxa
ð2Þ-rhenað1Þ-cyclopentane ð3aÞ
159.0 mg (0.469 mmol) 1 and 46.5 ll (0.397 mmol) N
tert-butylamino ethanol (2c). Yield: 178 mg (0.230
1
90.9 mg (0.268 mmol) 1 and 21.4 ll (0.268 mmol) 2-
methylamino ethanol (2a). Yield: 90 mg (0.131 mmol,
mmol, 98%), colourless solid, m.p. >270 °C (dec.). H
NMR (399.79 MHz, CD2Cl2): d 1.50 (s, 18 H, CH3),
2.80–2.89 (m, 2 H, N–HCH), 3.54–3.62 (m, 2 H, N–
HCH), 3.71 (br, 2 H, N–H), 4.24–4.31 (m, 2 H, O–
1
98%), colourless solid, m.p. >220 °C (dec.). H NMR
(270.17 MHz, [D6]-acetone): d 2.65–2.74 (m, 2 H, N–
CH2), 3.28 (s, 6 H, N–CH3), 3.87–3.98 (m, 2 H, N–
1
HCH), 4.35–4.41 (m, 2 H, O–HCH). 13Cf Hg NMR
CH2), 4.18–4.38 (m, 4 H, O–CH2). 13Cf Hg NMR
(100.64 MHz, CD2Cl2): d 28.75 (C–ðCH3Þ3), 45.67 (N–
CH2), 57.39 ðC–ðCH3Þ3Þ, 76.82 (O–CH2), 196.16,
198.29, 206.34 (CO). IR (KBr) [cmÀ1]: 3238.3 s (m N–H),
3018.5 w, 2981.9 s (m CH2), 2930.7 m (m CH2), 2886.7 s (m
CH2), 2007.4 vs (m CO, a1), 1877.6 vs (m CO, e), 1631.2 m
(d NH), 1477.8 vs (d CH2), 1466.3 s (d CH2), 1397.1 vs (d
C(CH3Þ3), 1379.0 s (d C(CH3Þ3), 1194.3 s, 1137.6 s,
1086.0 vs, 1041.5 s, 1015.0 m, 916.6 m, 879.9 m, 666.0 m,
652.6 m, 590.9 m, 562.4 m, 535.6 vs, 507.9 s, 478.9 s,
437.8 m, 396.3 m, 343.0 m. IR (CH2Cl2) [cmÀ1]: 2010.4
vs (m CO, a1), 1895.3 vs (m CO, e). Anal. found: C,
27.74%; H, 3.39%; N, 3.59%. Calc. for C18H28N2O8Re2
(772.85 g/mol): C, 27.97%; H, 3.65%; N, 3.63%. MS
(DEI) m=z (%): 772 (46) [Mþ], 744 (80) [Mþ–CO], 716
(14) [Mþ–2 CO], 688 (7) [Mþ–3 CO], 660 (21) [Mþ–4
CO], 632 (8) [Mþ–5 CO], 604 (10) [Mþ–6 CO].
1
(67.94 MHz, [D6]-acetone): d 44.89 (N–CH3), 53.17 (N–
CH2), 78.73 (O–CH2), 196.63, 196.99, 198.80 (CO). IR
(KBr) [cmÀ1]: 3266.2 s (m N–H), 2985.3 w (mCH2), 2947.1
m (m CH2), 2923.5 m (mCH2), 2876.5 s (m CH2), 2817.7 w
(m N–CH3), 2361.7 m, 2332.3 m, 2011.9 vs (m CO, a1),
1885.3 vs (m CO, e), 1475.3 s (dCH2), 1463.4 m (d CH2),
1422.8 m, 1404.5 m, 1355.1 w, 1288.5 w, 1188.1 m,
1083.0 s, 1068.0 m, 1039.3 s (m C–O), 982.8 m, 884.1 s,
667.2 m, 644.2 m, 551.4 s, 514.7 s, 491.2 s, 358.5 w. IR
(CH2Cl2) [cmÀ1]: 2011.0 vs (m CO, a1), 1898.2 vs (m CO,
e). Anal. found: C, 21.21%; H, 2.37%; N, 3.85%. Calc.
for C12H16N2O8Re2 (688.69 g/mol): C, 20.93%; H,
2.34%; N, 4.07%. MS (DEI) m=z (%): 688.5 (64) [Mþ],
660.6 (72) [Mþ–CO], 632.6 (24) [Mþ–2 CO], 604.5 (30)
[Mþ–3 CO], 576.5 (61) [Mþ–4 CO], 548.5 (22) [Mþ–5
CO], 345.4 (15) [Mþ/2+H].
3.1.4. trans-Bis½1,1,1-tricarbonyl-5-phenyl-azað5Þ-l-oxað2Þ-
rhenað1Þ-cyclopentane ð3dÞ
3.1.2. trans-Bis½1,1,1-tricarbonyl-5-ethyl-azað5Þ-l-oxað2Þ-
rhenað1Þ-cyclopentane ð3bÞ
114.5 mg (0.337 mmol) 1 and 42.1 ll (0.337 mmol) 2-
anilino ethanol (2d). Yield: 132 mg (0.162 mmol, 96%),
109.9 mg (0.324 mmol) 1 and 29.3 ll (0.300 mmol) 2-
ethylamino ethanol (2b). Yield: 100 mg (0.140 mmol,
1
colourless solid, m.p. >230 °C. H NMR (270.17 MHz,
1
86%), colourless solid, m.p. >250 °C (dec.). H NMR
CD2Cl2): d 3.35–3.52 (m, 2 H, N–HCH), 4.02–4.15 (m, 2
H, N–HCH), 4.41–4.65 (m, 4 H, O–CH2), 7.43–7.55 (m,
3
(400.18 MHz, CD2Cl2): d 1.44 (t, 6 H, J ¼ 7:12 Hz,
1
NH–CH2–CH3), 2.66–2.75 (m, 2 H, NH–HCH–CH2–
O), 3.28–3.38 (m, 2 H, NH–HCH–CH3), 3.46 (br, 2 H,
NH), 3.52–3.62 (m, 2 H, NH–HCH–CH3), 3.79–3.87
(m, 2 H, NH–HCH–CH2–O), 4.25–4.31 (m, 2 H, NH–
CH2–HCH–O), 4.34–4.40 (m, 2 H, NH–CH2–HCH–O).
10 H, Ar–H). 13Cf Hg NMR (67.93 MHz, CD2Cl2): d
53.80 (N–CH2), 78.44 (O–CH2), 121.27 (o–Ar–C),
126.71 (p–Ar–C), 130.11 (m–Ar–C), 147.35 (Ar–Cq). IR
1
13Cf Hg NMR (100.64 MHz, CD2Cl2): d 15.03 (NH–
CH2–CH3), 50.89 (NH–CH2–CH2–O), 52.07 (NH–
CH2–CH3), 77.82 (NH–CH2–CH2-O), 196.29 (CO),
197.45 (CO), 198.33 (CO). IR (KBr) [cmÀ1]: 3248 m
(m NH), 2965 w (m CH2), 2894 m (m CH2), 2006 vs (m CO,
a1), 1889 vs (m CO, e), 1870 vs (m CO, e), 1622 w, 1473 m
(d CH2), 1455 w, 1411 m, 1249 w, 1182 w, 1125 w, 1090
m, 1051 s, 898 m, 810 w, 664 w, 549 m, 536 w, 510 m,
489 m, 385 w. IR (CH2Cl2) [cmÀ1]: 2010 vs (m CO, a1),
1896 vs (m CO, e). Anal. found: C, 23.47%; H, 2.78%; N,
Scheme 1. Synthesis of 3a–f.