Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
400 MHz): δ = 0.94 (m, 3 H), 1.35 (s, 6 H), 1.50 (m, 6 H) ppm. 13C for 1 h, treated drop wise with stirring within 1 h with a solution of
NMR (CDCl3. 20 °C, 101 MHz): δ = 13.76, 22.60, 26.57, 27.29, 32.26 valeronitrile (14.2 g, 174 mmol) and 1-bromobutane (95.0 g,
(s), 40.71, 125.07 (s, CN) ppm.
695 mmol) in anhydrous ether (150 mL), stirred for 1 h, allowed to
warm to room temperature while evaporating the ammonia (5 h),
treated with anhydrous ether (250 mL), stirred for 1 d, treated drop
wise with anhydrous ethanol (50 mL) for the degradation of residual
sodium amide, hydrolyzed with distilled water, acidified with 2 n sul-
furic acid separated from the aqueous phase with extraction of the
latter (3ϫ50 mL), dried with magnesium sulfate, evaporated and dis-
2,2-Dimethylheptanenitrile (7): Sodium metal (18.0 g, 785 mmol)
was dissolved in liquid ammonia (250 mL), treated with the amount
of a micro spatulum of iron(III)nitrate, allowed to stand for 1 h, treated
drop wise with stirring within 1 h with a solution of isobutyronitrile
(34.5 g, 500 mmol) and 1-bromopentane (98.2 g, 650 mmol) in anhy-
drous ether (150 mL), stirred for 1 h, allowed to warm to room tem-
perature while evaporating the ammonia (5 h), treated with anhydrous
ether (250 mL), stirred for 1 d, treated drop wise with anhydrous eth-
anol (50 mL) for the degradation of residual sodium amide, hydrolyzed
with distilled water, acidified with 2 n sulfuric acid separated from the
aqueous phase with extraction of the latter (3ϫ50 mL), dried with
magnesium sulfate, evaporated and distilled. Yield 36.4 g (52%), b.p.
20
tilled. Yield 15.3 g (46%), b.p. 117–119 °C/24 mbar, nD = 1.4381.
IR (film): ν˜ = 2960 (s), 2930 (s), 2860 (s), 2225 (m, CN), 1470 (s),
1380 (m), 1345 (w), 1105 (w), 935 (w), 900 (w), 790 (w), 735 (m)
cm–1. 13C NMR (CDCl3. 20 °C, 101 MHz): δ = 13.88, 14.21, 17.66,
22.87, 26.45, 35.93, 38.44, 40.62 (s), 124.37 (s, CN) ppm.
20
72–74 °C/24 mbar, nD = 1.4167. IR (film): ν˜ = 2970 (s), 2940 (s),
Preparation of the Nitrile Complexes
2870 (s), 2240 (m, CN), 1470 (s), 1395 (m), 1375 (m), 1240 (w), 1215
1
(w), 735 (w) cm–1. H NMR (CDCl3, 20 °C, 400 MHz): δ = 0.90 (m,
The starting complexes CpFe(CO)(PPh3)I[29] and CpRu(CO)(PPh3)Cl[30]
were prepared as described.
3 H), 1.33 (s, 6 H), 1.49 (m, 8 H) ppm. 13C NMR (CDCl3. 20 °C,
101 MHz): δ = 13.76, 22.27, 24.75, 26.51, 31.63, 32.23 (s), 40.93,
124.98 (s, CN) ppm.
General Method for the Preparation of the Iron Complexes 1a,
3a–11a, and 12: To a suspension of CpFe(CO)(PPh3)I (118 mg,
0.22 mmol) and AgBF4 (44 mg, 0.22 mmol) in dichloromethane
(5 mL) the corresponding nitrile (0.22 mmol) was added. The mixture
was stirred under exclusion of light at room temperature for 20 min,
whereby the dark green suspension quickly turned to dark red. AgI
was separated by centrifugation and the solvent was removed in vacuo
from the solution. The residue was washed with ethyl ether, then with
n-pentane. All the iron complexes are brick colored and stable on air.
2-Cyclohexyl-2-methylpropionitrile (8): Sodium metal (18.0 g,
785 mmol) was dissolved in liquid ammonia (250 mL), treated with
the amount of a micro spatulum of iron(III)nitrate, allowed to stand
for 1 h, treated drop wise with stirring within 1 h with a solution of
isobutyronitrile (34.5 g, 500 mmol) and 1-bromocyclohexane (106 g,
650 mmol) in anhydrous ether (150 mL), stirred for 1 h, allowed to
warm to room temperature while evaporating the ammonia (5 h),
treated with anhydrous ether (250 mL), stirred for 1 d, treated drop
wise with anhydrous ethanol (50 mL) for the degradation of residual
sodium amide, hydrolyzed with distilled water, acidified with 2 n sul-
furic acid separated from the aqueous phase with extraction of the
latter (3ϫ50 mL), dried with magnesium sulfate, evaporated and dis-
(Carbonyl)(cyclopentadienyl)(1-ethylcyclohexanecarbonitrile)(tri-
phenylphosphine)iron-tetrafluoroborate (1a): Yield 127 mg (88%).
M.p. 135 °C (dec.). IR (KBr): ν˜ = 2261w (CN), 1980s (CO), 1055vs,br
(BF4) cm–1. 1H NMR ([D6]acetone, 270 MHz): δ = 0.79 (t, J = 7.5 Hz,
3 H, CH3), 1.00–1.71 (m, 24 H,CH2), 1.41 (q, J = 7.5 Hz, 2 H,
CH2CH3), 5.09 (d, J = 1.5 Hz, 5 H, Cp), 7.43–7.67 (m, 15 H, PPh3)
ppm. 31P NMR ([D6]acetone, 109.4 MHz): δ = 66.84 (s) ppm.
C33H35BF4FeNOP·0.25CH2Cl2 (656.5) : calcd. C 60.83, H 5.45, N
2.13%; found C 60.35, H 5.88, N 2.35%.
20
tilled. Yield 34.5 g (46%), b.p. 165–166 °C/27 mbar, nD = 1.4577.
IR (film): ν˜ = 2980 (s), 2930 (s), 2850 (s), 2230 (m, CN), 1450 (s),
1390 (m), 1370 (m) 1255 (m), 1220 (w), 1200 (m), 1030 (w), 900 (m),
1
850 (w), 690 (w) cm–1. H NMR (CDCl3, 20 °C, 400 MHz): δ = 1.19
(m, 1 H), 1.33 (s, 6 H), 1.83 (m, 10 H) ppm. 13C NMR (CDCl3. 20 °C,
101 MHz): δ = 27.42, 25.96, 26.29, 27.90, 36.26 (s), 45.83, 124.95 (s,
CN) ppm.
(Carbonyl)(2-butyl-2-methylhexanenitrile)(cyclopentadienyl)(tri-
phenylphosphine)iron-tetrafluoroborate (3a): Yield 130 mg (89%).
M.p. 124 °C (dec.). IR (KBr): ν˜ = 2264w (CN), 1979s (CO), 1054
vs,br (BF4) cm–1. 1H NMR ([D6]acetone, 270 MHz); δ = 0.85,0.92 (t,
J = 7.1 Hz, 6 H, CH3), 1.08. 1.10 (s, 3 H,CCH3), 1.13–1.34 (m, 12 H,
CH2), 5.07 (s, 5 H,Cp), 7.35–7.64 (m, 25 H, PPh3) ppm. 13C NMR-
(acetone-D6, 100.5 MHz): δ = 9.90, 18.91 (CH3), 18.99, 19.19, 23.36,
23.41, (CH2), 23.50 (CCH2), 34.58 (CCH3), 34.94, 36.56 (CCH2),
81.78 (Cp), 126.07 (d, J = 10.0 Hz, m) 128.27 (s, p), 129.22(d, J =
46.4 Hz, I), 129.99 (d, J = 10.5 Hz,o), 140.41 (CN) ppm. 31P NMR
([D6]acetone, 109.4 MHz): δ = 67.16 (s) ppm. C35H41BF4FeNOP·0.25
CH2 Cl2 (686.6): calcd. C 61.67, H 6.09, N 2.04%; found C 61.90, H
5.83, N 2.65%.
2,2-Dipentyl-heptanenitrile (9): Sodium metal (30.0 g, 1.3 mol) was
dissolved in liquid ammonia (250 mL), treated with the amount of a
micro spatulum of iron (III)nitrate, allowed to stand for 1 h, treated
drop wise with stirring within 1 h with a solution of acetonitrile
(12.25 g, 300 mmol) and 1-brompentane (179.7 g, 1.19 mol) in anhy-
drous ether (150 mL), stirred for 1 h, allowed to warm to room tem-
perature while evaporating the ammonia (5 h), treated with anhydrous
ether (250 mL), stirred for 1 d, treated drop wise with anhydrous eth-
anol (50 mL) for the degradation of residual sodium amide, hydrolyzed
with distilled water, acidified with 2 n sulfuric acid separated from the
aqueous phase with extraction of the latter (3ϫ50 mL), dried with
magnesium sulfate, evaporated and distilled. Yield 56.2 g (75%), b.p.
20
108–110 °C/0.53 mbar, nD = 1.4448. IR (film): ν˜ = 2980 (s), 2940
(Carbonyl)(cyclopentadienyl)(2,2-dibutylhexanenitrile)(triphenyl-
phosphine)iron-tetrafluoroborate (4a): Yield 153 mg (87%). M.p.
141 °C (dec.). IR (KBr): ν˜ = 2267vw (CN), 1976s (CO), 1052vs,br
(BF4) cm–1. 1H NMR ([D6]acetone, 270 MHz): δ = 0.84 (m, 9 H,
CH2CH3); 1.14–1.44 (m, 18 H, CH2), 5.07 (d, J = 1.4 Hz, 5 H), 7.21–
(s), 2870 (s), 2230 (m, CN), 1465 (s), 1385 (m), 1160 (w), 1115 (w),
730 (w) cm–1. 1H NMR (CDCl3, 20 °C, 400 MHz): δ = 0.90 (m, 9 H),
1.30 (m, 24 H) ppm. 13C NMR (CDCl3. 20 °C, 101 MHz): δ = 13.94,
22.42, 23.93, 31.90, 36.11, 40.62 (s), 124.34 (s, CN) ppm.
2-Butyl-2-propylhexanenitrile (10): Sodium metal (18.0 g, 7.69 (m, 15 H) ppm. 31P NMR ([D6]acetone, 109.4 MHz): δ =
785 mmol) was dissolved in liquid ammonia (250 mL), treated with 66.92 ppm. C38H47BF4FeNOP·CH2Cl2 (792.4): Calcd. C 59.12, H
the amount of a micro spatulum of iron(III)nitrate, allowed to stand 6.23, N 1.77; found C 59.92, H 6.25, N 1.55.
Z. Anorg. Allg. Chem. 2017, 1262–1268
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim