592
T. Blo¨mker et al. · Ferrocenyl-capped Long-chain Alkynes
68.8 (Cp), 68.3 (C2, C5), 67.5 (C3, C4), 31.0 (C7), 29.7 (C6), M. p. 57.7 ◦C. – C32H38Fe2 (534.33): calcd. C 71.93, H 7.17;
28.9 (C8), 28.6 (C9), 18.6 (C10). – HRMS ((+)-ESI): m/z = found C 71.58, H 7.06.
280.0916 (calcd. 280.0909 for C17H20Fe, [M]+). – IR (film):
ν = 3303 (m), 3093 (w), 2933 (s), 2858 (m), 1457 (w), 1436
2
[η -1,12-Diferrocenyldodec-6-yne]hexacarbonyl-
(w), 1105 (m), 1000 (m), 816 (s), 627 (vs) cm−1. – C17H20Fe
dicobalt (12)
(280.19): calcd. C 72.87, H 7.19; found C 72.78, H 7.33.
The ferrocenylalkyne 3 (100 mg, 0.19 mmol) was dis-
1,12-Diferrocenyldodeca-5,7-diyne (4)
solved in 15 mL diethyl ether. Subsequently, a solution of
dicobaltoctacarbonyl (96.1 mg, 0.28 mmol, 1.5 eq.) in 10 mL
ether was added. The reaction mixture was stirred overnight
before the solvent was removed in vacuo. The crude product
was dissolved again in 10 mL pentane and filtered through a
short pack of silica gel (eluent: pentane/diethyl ether, 95/5).
After removal of solvent 12 was obained as a dark solid
(66.1 mg, 84 %). Single crystals suitable for the X-ray crystal
structure determination were grown from a saturated solution
of 12 in pentane at −30 ◦C. – 1H NMR (599.6 MHz, 298 K,
[D6]benzene): δ = 4.03 (s, 10H, Cp), 3.99 (m, 4H, (2-H,
5-H)), 3.97 (m, 4H, (3-H, 4-H)), 2.64 (m, 4H, 10-H), 2.28 (pt,
4H, 6-H), 1.59 (m, 4H, 9-H), 1.47 (m, 4H, 7-H), 1.30 (m, 4H,
The terminal acetylene 8 (300 mg, 1.13 mmol) was dis-
solved in acetonitrile (15 mL), and copper acetate (1.62 g,
8.12 mmol, 7.2 eq.) was added. After refluxing the reac-
tion mixture for 7 h the solvent was removed in vacuo.
The remaining solid was directly submitted to column chro-
matography (silica gel, eluent: pentane/toluene, 8/2) to yield
the diyne 4 (294 mg, 97 %) as a yellow solid. Single crys-
tals suitable for the X-ray crystal structure determination
were obtained by slow evaporation of a saturated solution
of 4 in dichloromethane. – 1H NMR (499.8 MHz, 298 K,
[D6]benzene): δ = 4.00 (s, 10H, Cp), 3.93 (pt, 4H, (3-
H, 4-H)), 3.89 (pt, 4H, (2-H, 5-H)), 2.07 (m, 4H, 6-H),
1
8-H). – 13C { H} NMR (150.8 MHz, 298 K, [D6]benzene):
3
1.95 (t, JH,H = 7.0 Hz, 4H, 9-H), 1.45 (m, 4H, 7-H),
δ = 200.8 (CO), 100.2 (C11), 89.0 (C1), 68.8 (Cp), 68.5
(C2, C5), 67.6 (C3, C4), 34.2 (C10), 32.0 (C9), 31.4 (C7),
30.0 (C6), 29.5 (C8). – HRMS ((+)-ESI): m/z = 820.0013
(calcd. 820.0027 for C38H38Co2Fe2O6, [M]+). – IR (film):
ν = 2936 (s), 2907 (w), 2085 (s), 2022 (sh), 2012 (vs),◦1983
(vs), 1106 (s), 1002 (s), 829 (s) cm−1. – M. p. 52.9 C. –
C38H38Co2Fe2O6 (764.42): calcd. C 55.64, H 4.67; found
C 55.40, H 4.26.
1
1.30 (m, 4H, 8-H). – 13C { H} NMR (125.7 MHz, 298 K,
[D6]benzene): δ = 89.0 (C1), 77.0 (C10), 68.8 (Cp), 68.3
(C2, C5), 67.5 (C3, C4), 66.8 (C11), 30.4 (C7), 29.1 (C6),
28.3 (C8), 19.2 (C9). – MS (MALDI): m/z (%) = 529.8
(100) [C32H34Fe2]+. – M. p. 84.3 ◦C. – C32H34Fe2 (530.30):
calcd. C 72.48, H 6.46; found C 72.67, H 6.55.
1,12-Diferrocenyldodec-6-yne (3)
2
2
(6-Heptynyl)ferrocene (150 mg, 0.54 mmol) was dis-
solved in 15 mL thf at 0 C and deprotonated by addition
of n-butyllithium (0.37 mL of a 1.6 M solution in pentane,
0.54 mmol, 1 eq.). After 1 h a solution of 11 (205 mg,
[η , η -1,12-Diferrocenyldodeca-5,7-diyne]bis(hexa-
carbonyldicobalt)] (13)
◦
1,12-Diferrocenyldodeca-5,7-diyne (4) (100 mg,
0.54 mmol, 1 eq.) in 5 mL thf was added, and the mix- 0.21 mmol) was dissolved in 20 mL diethyl ether and
ture was stirred overnight while warming to r. t. The reac- treated with dicobaltoctacarbonyl (160 mg, 0.46 mmol,
tion was stopped by adding 50 mL water and 50 mL pen- 2.2 eq.). The reaction mixture was stirred overnight before
tane. Layers were separated, and after extraction of the the solvent was removed in vacuo. The crude product
aqueous layer with pentane (2 × 50 mL) the combined or- was submitted to column chromatography (silica gel,
ganic layers were dried over MgSO4. The crude product eluent: pentane/diethyl ether 95/5). After removing the
was purified by column chromatography at silica gel (elu- solvent 13 (150 mg, 67 %) was obtained as a dark brown
ent: pentane/dichloromethane, 95/5 → 80/20). Compound 3 solid. Crystals suitable for the X-ray crystal structure
was obtained as an orange solid (150 mg, 52 %). – 1H NMR determination were grown from a saturated solution of 13
(599.6 MHz, 298 K, [D6]benzene): δ = 4.01 (s, 10H, Cp), in dichloromethane by slow evaporation of the solvent. –
3.96 (m, 8H, (2-H to 5-H)), 2.22 (pt, 4H, 6-H ), 2.15 (t, 1H NMR (599.6 MHz, 298 K, [D6]benzene): δ = 4.01 (s,
3JHH = 6.9 Hz, 4H, 10-H), 1.48 (m, 4H, 9-H), 1.45 (m, 4H, 10H, Cp), 3.98 (m, 4H, (2-H, 5-H)), 3.97 (m, 4H, (3-H,
1
7-H), 1.41 (m, 4H, 8-H). – 13C { H} NMR (150.8 MHz, 4-H)), 2.87 (m, 4H, 9-H), 2.32 (pt, 4H, 6-H), 1.79 (m, 4H,
1
298 K, [D6]benzene): δ = 89.3 (C1), 80.5 (C11), 68.8 (Cp), 8-H), 1.59 (m, 4H, 7-H). – 13C { H} NMR (150.8 MHz,
68.4 (C2, C5), 67.5 (C3, C4), 31.2 (C7), 29.8 (C6), 29.4 (C9), 298 K, [D6]benzene): δ = 199.7 (CO), 106.7 (C10),
29.1, (C8), 19.2 (C10). – HRMS ((+)-ESI): m/z = 534.1662 91.9 (C11), 88.5 (C1), 68.9 (Cp), 68.4 (C2, C5), 67.7
(calcd. 534.1668 for C32H38Fe2, [M]+). – IR (film): ν = (C3, C4), 33.8 (C9), 32.0 (C8), 31.5 (C7), 29.8 (C6). –
3101 (w), 2929 (m), 2855 (m), 2361 (w), 1466 (m), 1090 HRMS ((+)-ESI): m/z = 1101.8078 (calcd. 1101.8074
(s), 1044 (s), 1001 (s), 918 (m), 830 (vs), 821 (vs) cm−1. – for C44H34Co4Fe2O12
, – –
[M]+). M. p. 111.9 ◦C.
- 10.1515/znb-2009-0602
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