Organometallic Lewis Acids, Part LXII. Chiral Carbonyl-Cyclopentadienyl-Triphenylphosphine-Iron and -Ruthenium Complexes with Tertiary Nitriles [CpM(CO)(PPh3)(N≡C–CR1R2R3)]+ BF4–

Article abstract of DOI:10.1002/zaac.201700235

A series of tertiary nitriles was synthesized by alkylation of acetonitrile, primary and secondary nitriles, using alkylbromides and sodium amide in liquid ammonia. By reaction of the in situ formed organometallic Lewis acids [CpM(CO)(PPh₃)]

Full text of DOI:10.1002/zaac.201700235

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.201700235
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Organometallic Lewis Acids, Part LXII[1].
Chiral Carbonyl-Cyclopentadienyl-Triphenylphosphine-Iron and
-Ruthenium Complexes with Tertiary Nitriles [CpM(CO)(PPh3)
(NϵC–CR1R2R3)]+ BF4 (M = Fe, Ru)
–
Christopher U. Missling,[a] Karlheinz Sünkel,[a] Heinz Langhals,*[a] and Wolfgang Beck*[a]
Dedicated to Professor Gottfried Huttner on the Occasion of his 80th Birthday
Abstract. A series of tertiary nitriles was synthesized by alkylation of
acetonitrile, primary and secondary nitriles, using alkylbromides and
sodium amide in liquid ammonia. By reaction of the in situ
Fe, Ru) with the novel tertiary nitriles, the complexes
[CpM(CO)(PPh3)(NϵC–CR1R2R3]BF4 were obtained. A di-iron com-
plex was formed with 1,6-dicyanohexane.
formed organometallic Lewis acids [CpM(CO)(PPh3)]+ (M
=
Introduction
Results and Discussion
Chiral complexes of iron and ruthenium with four different
ligands CpM(CO)(PR3)X and [CpM(CO)(PR3)(L)]+ (M = Fe,
Ru)[2–6] and the Gladysz complexes [CpRe(NO)(PPh3)(L)]+[7]
have found high attention as inorganic counter parts of meth-
ane derivatives and very many examples have been reported.
Brunner was the first to accomplish chiral resolution of orga-
nometallic complexes with four different ligands.[8] Later on,
several other researchers also succeeded in separating and isol-
ating the enantiomers, which could be used as optically active
auxiliaries in asymmetric organic synthesis[9,10]
We prepared the tertiary nitriles by alkylation of acetonitrile,
primary and secondary nitriles, respectively. Various methods
for the alkylation of nitriles were reported such as in the begin-
ning a favored intramolecular ring closure.[15] The alkylation
of nitriles, preferentially activated by phenylsubstituents, by
means of an oil suspension of sodium amide in liquid ammonia
was reported,[16] however proved to be comparatively compli-
cated and gave a mixture of alkylation products. The applica-
tion of potassium amide instead sometimes lead to partial loss
of the nitrile group.[17] A further method for the alkylation by
means of a slurry of sodium amide in ether was described[18]
and also gave a mixture of alkylation products. We found the
combination of the method of Bergstrom and Agostinho[16]
with the method of Schurch and Huntress[18] proved to be very
satisfying and useful for upscaling. Thus, sodium metal was
dissolved in liquid ammonia, converted to sodium amide by
means of iron(III) and allowed to react with the corresponding
nitrile and alkyl bromide in plenty of anhydrous ethyl ether,
while increasing the temperature to ambient. The released gas-
eous ammonia can be recovered by condensing for cascading
batches. Finally, the nitriles were isolated in sufficient purity
after aqueous work-up and vacuum distillation. The tertiary
nitriles form thermally stable colorless liquids, where three
flexible alkyl chains provide both shielding of the nitrile car-
bon and good solubility; the latter is useful for the preparation
of nitrile metal complexes (see Scheme 1).
In the following we report on chiral iron and ruthenium
complexes with
a
series of novel tertiary nitriles
[CpM(CO)(PPh3)(NϵC–CR1R2R3)]+, and with a long chain
alkylcyanide. Sterically shielded tertiary nitriles are of interest
for special applications because the electrophilic carbon atom
of the nitrile group is masked, whereas the nucleophilic nitro-
gen atom is still well-accessible such as for complexing with
Lewis acids. As a consequence, such nitriles are very resistant
to alkaline hydrolysis[11] and more general to the attack of nu-
cleophiles. Moreover, the lack of enolizable hydrogen atoms
renders these substances to be robust reagents both under
strongly alkaline and acidic media.
Organometallic cyclopentadienyl iron and ruthenium nitrile
complexes have found interest as possible materials for non-
linear optics,[12] as compounds with liquid-crystalline proper-
ties[13] and for use in Langmuir-Blodgett films.[14]
The chiral cationic nitrile complexes of the type
[CpM(CO)(PR3)(NCRЈ)]+ (M = Fe, Ru; “Cp” = substituted or
unsubstituted cyclopentadienyl) were prepared before, usually
by halide abstraction from the corresponding halide complexes
[CpM(CO)(PR3)(X)] (X = Cl, Br, I) by means of AgI salts in
the presence of the corresponding nitriles (see Scheme 2).
Using a chiral neomenthyl substituent on the cyclopentadienyl
* Prof. Dr. H. Langhals
E-Mail: Langhals@lrz.uni-muenchen.de
* Prof. Dr. W. Beck
E-Mail: wbe@cup.uni-muenchen.de
[a] Department Chemie
Ludwig-Maximilians-Universität München
Butenandtstr. 5–13
81377 München, Germany
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Scheme 3. The dinuclear complex 12 (one stereoisomer is shown).
The reactions were performed in dichloromethane. How-
ever, in contrast to reactions of the isosteric rhenium Lewis
acid [CpRe(CO)(PPh3)]+, where the dichloromethane complex
[CpRe(CO)(PPh3)(ClCH2Cl)]+ is formed,[25,26] “no evidence
for a dichloromethane adduct” was observed with the iron and
ruthenium compounds.[20] This observation can be certainly
attributed to the stronger rhenium Lewis acidity – due to the
stronger acceptor ability of the NO ligand – in comparison to
the iron and ruthenium CO analogues. However, it should be
noted that isolation of the methyl iodide complex
[CpRu(CO)(PPh3)(IMe)]+ is possible; addition of MeCN to
this compound leads to substitution of MeI by the nitrile.[20]
The complexes 1–12 are characterized by their CN and CO
IR absorptions at 2295–2242 cm–1 and 1970–1980 cm–1,
respectively, and a broad BF4 absorption at 1055 cm–1. In
many cases the diastereotopic groups can be detected in the
1H and 13C NMR spectra (see Experimental Section).
Scheme 1. The alkylnitriles 1 to 11 applied as ligands.
ring allowed the separation of the chiral-at-metal MeCN com-
plexes.[21] Nitriles used in these reactions include MeCN, ole-
finic and aromatic nitriles as well as cyanoacetic methyles-
ter.[5,22,23] Quite interesting, it was not successful to obtain the
corresponding Ru complex with the long chain nitrile
C18H37CN by this method, whereas the reaction of the more
electron rich [CpRu(PR3)2Cl] proceeded without difficulty.[14]
A rather unusual synthesis of [CpFe(CO)(PPh3)(MeCN)]+
Molecular Structure of 4b
Compound 4b crystallizes in the centrosymmetric mono-
clinic space group P21/c; therefore, both enantiomers of the
chiral pseudo-tetrahedral cation can be found in the unit cell
(Figure 1). The bond lengths and angles are similar to the ones
found in the three crystallographically characterized
[CpRu(CO)(PR3)(NCMe)]+ complexes (Ru–N: 2.049–2.074 Å;
Ru–C: 1.855–1.870 Å; Ru–P: 2.324–2.351 Å; Ru–Cp: 1.868–
used
the
reaction
of
the
vinylidene
complex
[CpFe(CO)(PPh3)(=C=CH2)]+ with hydrazine derivatives.[19]
In our laboratory the “organometallic Lewis acids“
[CpM(CO)(PPh3)]+ (M = Fe, Ru) and [Re(CO)5]+ were added
to the nitrile groups of CpFe–(CH2)nCϵN (n = 1,2) to give
cationic dinuclear complexes.[24]
Scheme 2. Synthesis of nitrile complexes: (i) M = Fe; 1a, 3a – 11a;
X = I. (ii) M = Ru; 2b – 6b, 11b; X = Cl.
The in situ – from CpM(CO)(PPh3)X (M = Fe, Ru; X = Cl,
I) and AgBF4 – formed “organometallic Lewis acids”
[CpM(CO)(PPh3)]+ react with the novel tertiary nitriles to af-
ford the iron complexes 1a, 3a–10a and the ruthenium com-
pounds 2b–6b (see Scheme 2). With CH3(CH2)11CN the com-
plexes 11a and 11b are formed and with 1,6-dicyanohexane
the dinuclear iron complex 12 could be obtained (see
Scheme 3). The iron complexes are isolated as deep red, the
ruthenium complexes as yellow compounds.
Figure 1. ORTEP3 view (30% probability ellipsoids) of the cation of
complex 4b. Selected bond lengths /Å and angles /°: Ru–P: 2.319(5);
Ru–N: 1.990(17); Ru–C1: 1.86(2); Ru–Cp: 1.858(10); N–C25: 1.13(2);
C25–N–Ru: 174.4(17); N–C25–C26: 177(2).
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ether (250 mL), stirred for 1 d, treated drop wise with anhydrous eth-
1.883 Å; C–N–Ru: 173.1–178.5°; and N–C–C: 176.4–
178.8°).[21,27,28] The longer Ru–N bond reflects the steric de-
mands of the tertiary alkyl group. As is observed quite often
with similar compounds, the three butyl groups exhibit severe
disorder in the two “terminal” carbon atoms, and the BF4 anion
is also heavily disordered. The crystal structure contains ap-
proximately 3.7% solvent accessible voids, which are probably
filled by the CH2Cl2 crystallization solvent, which is most
likely severely disordered and could not be localized. Due to
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 20.8 g (71%), b.p.
101–102 °C/24 mbar, nD20 = 1.4294. IR (film): ν˜ = 2960 (s), 2940 (s),
2860 (s), 2230 (m, CN), 1725 (w), 1470 (s), 1380 (m), 1345 (w), 1295
(w), 735 (w) cm–1. 13C NMR (CDCl3. 20 °C, 101 MHz): δ = 13.79,
22.75, 23.93, 26.90, 36.59 (s), 39.14, 124.55 (s, CN) ppm. C11H21N
(167.3): calcd. C 78.97, H 12.65, N 8.37%; found C 78.28, H 12.91,
these disorders, and the relative weak reflections at larger 2Θ N 8.61%.
angles, only some atoms could be refined anisotropically and
thus, rather poor R values could be obtained in the refinement.
2,2-Dibutylhexanenitrile (4): Sodium metal (30.0 g, 1.3 mol) was dis-
solved 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-brombutane (163 g, 1.19 mol) 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 sulfuric acid separated from the aqueous
phase with extraction of the latter (3ϫ50 mL), dried with magnesium
sulfate, evaporated and distilled. Yield 40.14 g (64%), b.p. 105–
Experimental Section
Preparation of the Tertiary Nitriles
1-Ethylcyclohexanecarbonitrile (1): 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
cyclohexanecarbonitrile (46 g, 421 mmol) and 1-bromoethane (59.6 g,
547 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-
20
106 °C/1.3 mbar, nD = 1.4404. IR (film): ν˜ = 2980 (s), 2940 (s),
2870 (s), 2230 (m, CN), 1465 (s), 1380 (m), 1345 (w), 1265 (w), 1105
1
(w), 900 (w), 735 (w) cm–1. H NMR (CDCl3, 20 °C, 400 MHz): δ =
0.94 (m, 9 H), 1.43 (m, 18 H) ppm.
2,2-Dimethylpentanenitrile (5): 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-bromopropane (80 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 35.1 g (63%), b.p.
20
tilled. Yield 25.2 g (44%), b.p. 105–107 °C/24 mbar, nD = 1.4518.
IR (film): ν˜ = 2970 (s), 2930 (s), 2860 (s), 2230 (m, CN), 1455 (s),
1390 (m), 1075 (w), 1000 (m), 945 (m), 905 (m), 850 (w), 780 (w)
cm–1. 1H NMR (CDCl3, 20 °C, 400 MHz): δ = 0.95–2.05 (m) ppm.
13C NMR (CDCl3. 20 °C, 101 MHz): δ = 8.76, 23.12, 25.54, 33.41,
35.32, 39.62 (s), 123.58 (s, CN) ppm.
1-Propylcyclohexanecarbonitrile (2): 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
cyclohexanecarbonitrile (46 g, 421 mmol) and 1-bromopropane
(67.3 g, 547 mmol) in anhydrous ether (150 mL), stirred for 1 h, al-
lowed 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 resid-
ual 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 dis-
20
41–43 °C/24 mbar, nD = 1.4033. IR (film): ν˜ = 2970 (s), 2940 (s),
2880 (s), 2240 (m, CN), 1470 (m), 1460 (m), 1395 (w), 1375 (w),
1270 (w), 1220 (w), 1205 (w), 750 (w) cm–1. 1H NMR (CDCl3, 20 °C,
400 MHz): δ = 0.96 (m, 3 H), 1.31 (s, 6 H), 1.49 (m, 4 H) ppm. 13C
NMR (CDCl3. 20 °C, 101 MHz): δ = 13.97, 18.48, 26.59, 32.29 (s),
43.19, 125.09 (s, CN) ppm. C7H13N (111.2): calcd. C 75.61, H 11.79,
N 12.60%; found C 75.83, H 11.60, N 12.63%.
2,2-Dimethylhexanenitrile (6): 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-bromobutane (89 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
20
tilled. Yield 43.5 g (68%), b.p. 94–96 °C/24 mbar, nD = 1.4541. IR
(film): ν˜ = 2960 (s), 2940 (s), 2860 (s), 2230 (m, CN), 1470 (m), 1455
(s), 1385 (w), 1115 (w), 975 (w), 940 (w), 850 (w), 745 (w) cm–1. H
1
NMR (CDCl3, 20 °C, 400 MHz): δ = 0.88–2.05 (m) ppm. 13C NMR
(CDCl3. 20 °C, 101 MHz): δ = 14.09, 17.63, 22.99, 25.42, 35.66, 38.93
(s), 42.71, 123.68 (s, CN) ppm.
2-Butyl-2-methylhexanenitrile (3): Sodium metal (18.0 g, 785 mmol)
was dissolved in liquid ammonia (250 mL), treated with the amount distilled water, acidified with 2 n sulfuric acid separated from the
of a micro spatulum of iron(III)nitrate, allowed to stand for 1 h, treated aqueous phase with extraction of the latter (3ϫ50 mL), dried with
drop wise with stirring within 1 h with a solution of propionitrile magnesium sulfate, evaporated and distilled. Yield 39.5 g (63%), b.p.
20
(9.6 g, 174 mmol) and 1-bromobutane (95.0 g, 695 mmol) in anhy-
drous ether (150 mL), stirred for 1 h, allowed to warm to room tem-
65–66 °C/27 mbar, nD = 1.4109. IR (film): ν˜ = 2980 (s), 2960 (s),
2870 (s), 2235 (m, CN), 1470 (s), 1460 (s), 1395 (m), 1375 (m), 1250
perature while evaporating the ammonia (5 h), treated with anhydrous (w), 1210 (w), 1100 (w), 735 (w) cm–1. 1H NMR (CDCl3, 20 °C,
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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
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Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
(Carbonyl)(cyclopentadienyl)(2,2-dimethylpentanenitrile)(triphen-
3 1 P NMR ([D6 ]acetone, 109.4 MHz): δ = 67.47 (s) ppm.
ylphosphine)iron-tetrafluoroborate (5a): Yield 130 mg (90%). M.p. C36H43BF4FeNOP·CH2Cl2 (764.3): calcd. C 58.15, H 5.93, N 1.83%;
138 °C (dec.). IR(KBr): ν˜ = 2265vw (CN), 1974s (CO), 1055vs,br found C 59.45, H 5.57, N 1.33%.
(BF4)·cm–1. 1H NMR ([D6]acetone, 270 MHz): δ = 0.84 (t, J = 7.1 Hz,
1,6-Dicyanohexane-bis[(carbonyl)(cyclopentadienyl)(triphenyl-
phosphine)iron]-bis(tetrafluoroborate) (12): Yield 233 mg (84%).
M.p. 107 °C (dec.). IR (KBr): ν˜ = 2282 vw (CN), 1982 s (CO), 1054
vs, br (BF4) cm–1.– 1H NMR ([D6]acetone, 270 MHz): δ = 0.91–1,27
(m, 8 H, (CH2)4), 2.51 (m, 4 H, NCCH2 and CH2CN), 5.03 (d, J
= 1.4 Hz,10 H), 7.46–7.59 (m, 30 H) ppm. 31P NMR ([D6]acetone,
109.4 MHz): δ = 67.49 (s) ppm. C56H52B2F8Fe2N2O2P2·1.5CH2Cl2
(1259.7): calcd. C 54.83, H 4.40, N 2.22%; found C 54.93, H 4.68, N
3 H, CH2CH3), 1.08, 1.10 (s, 6 H, CCH3), 1.29–1.39 (m, 4 H, CH2),
5.07 (d, J = 1.4 Hz, 5 H), 7.43–7.67 (m, 15 H) ppm. 13C NMR (acet-
one-D6, 67.8 MHz): δ = 13.36 (CH2CH3),18.34 (CH2CH3),24.80,25.40
(C(CH3)2), 35.49 (C(CH3)2),41.94 (CCH2) ppm. 31P NMR ([D6]-
acetone, 109.4 MHz): δ = 67.52 (s) ppm. C31H33BF4FeNOP·0.5
CH2Cl2 (651.7): Calcd. C 58.06, H 5.26, N 2.15; found C 58.68, H
5.09, N 1.75.
(Carbonyl)(cyclopentadienyl)(2,2-dimethylhexanenitrile)(triphen- 2.27%.
ylphosphine)iron-tetrafluoroborate (6a): Yield 140 mg (95%). M.p.
General Method for the Preparation of the Ruthenium Complexes
133 °C. IR (KBr): ν˜ = 2264vw (CN), 1978s (CO), 1055vs.
(BF4) cm –1. 1H NMR ([D6]acetone, 270 MHz): δ = 0.86 (t, J = 6.2 Hz,
3 H, CH2CH3), 1.10 (s, 6 H, CCH3), 1.22–1.35 (m, 6 H, CH2),
5.09 (s, 5 H), 7.21–7.88 (m, 15 H) ppm. 31P NMR ([D6]acetone,
109.4 MHz): δ = 67.53 (s) ppm. C32H35BF4FeNOP·0.5 CH2Cl2
(665.7): calcd. C 58.64, H 5.45, N 2.10%; found C 58.81, H 5.25, N
1.74%.
2b–6b and 11b: To a suspension of CpRu(CO)(PPh3)Cl (108 mg,
0.22 mmol) and AgBF4 (45 mg, 0.23 mmol) in dichloromethane
(5 mL) the corresponding nitrile (0.22 mol) was added. The mixture
was stirred under exclusion of light for 45 min, whereby the yellow
color of the mixture became more intensive. AgCl was separated by
centrifugation and the solvent was removed in vacuo. The residue was
washed with ethyl ether and with n-pentane.The yellow complex was
dried in vacuo. It turned gradually brown, when exposed under argon
(Carbonyl)(cyclopentadienyl)(2,2-dimethylheptanenitrile)(triphen-
ylphosphine)iron-tetrafluoroborate (7a): Yield 131 mg (88%). M.p. to light.
119 °C (dec.). IR (KBr): ν˜ = 2266vw (CN), 1977s (CO), 1056vs,br
(BF 4) cm–1 1H NMR ([D6]acetone, 270 MHz): δ = 0.87 (t, J =
.
(Carbonyl)(cyclopentadienyl)(1-propylcycohexanecarbonitrile)
(triphenylphosphine)ruthenium-tetrafluoroborate (2b): Yellow
complex, which turns brown on light. Yield 137 mg (90 %). M.p.
153 °C (dec.). IR(KBr): ν˜ = 2266 w (CN), 1972 s (CO), 1054 br (BF4)
7.1 Hz, 3 H, CH2CH3), 1.09, 1.11 (s, 6 H, CCH3), 1.16–1.34 (m, 10
H, CH2), 5.07 (d, J = 1.4 Hz, 5 H), 7.25–7.88 (m, 15 H) ppm. 31P
N M R ( [ D 6 ] a c e t o n e , 1 0 9 . 4 M H z ) : δ = 6 7 . 4 9 ( s ) p p m .
C34H39BF4FeNOP·0.25CH2Cl2 (672.6): calcd. C 61.17, H 5.92, N
2.08%; found C 60.81, H 6.09, N 2.09%.
1
cm–1. H NMR ([D6]acetone, 270 MHz): δ = 0.84(t, J = 7 Hz), 3 H,
CH3), 0.92–1.73 (m. 14 H, CH2), 5.45 (s, 5 H, Cp), 7.45–7.79 (m, 15
H, Cp) ppm. 31P NMR ([D6]acetone, 109.4 MHz): δ = 49.58 (s) ppm:
C34H37BF4NOPRu: calcd. C 58.80, H 5.37, N 2.02%; found C 58.83,
(Carbonyl)(cyclopentadienyl)(2-cyclohexyl-2-methylpropionitrile)-
(triphenylphosphine)iron-tetrafluoroborate (8a): Yield 125 mg H 5.12, N 1.88%.
(87%). M.p. 113 °C(dec.). IR (KBr): = 2269vw (CN), 1983s (CO),
1057s,br (BF4) cm–1. 1H NMR ([D6]acetone, 270 MHz): δ = 1.06, 1.08
(s, 6 H, CCH3), 1.16–1.88 (m, 11 H, CH2 and CH), 5.06 (d, J = 1.3 Hz,
5 H), 7.41–7.68 (m, 15 H) ppm. 31P NMR ([D6]acetone, 109.4 MHz):
δ = 67.13 (s) ppm. C34H37BF4Fe NOP·1.5CH2Cl2 (776.7). calcd. C
54.90, H 5.19, N 1.80%; found C 54.79, H 5.09, N 2.04%.
(Carbonyl)(2-butyl-2-methylhexanenitrile)(cyclopentadienyl)(tri-
phenylphosphine)ruthenium-tetrafluorobore (3b): Yield 147 mg
(88). M.p. 98 °C (dec.). IR (KBr): ν˜ = 2267 vw (CN), 1981 s (CO),
1
1053 vs,br (BF4) cm–1. H NMR ([D6]acetone, 270 MHz): δ = 0.85,
0.86 (t, J = 7.2 Hz, 6 H, CH2CH3), 1.13 (s, 3 H, CCH3), 1.14–1.30
(m, 12 H, CH2), 5.42 (d, J = 0.3 Hz, 5 H), 7.38–7.65 (m, 15 H)
ppm. 31P NMR ([D6]acetone, 109.4 MHz): δ = 49.76 (s) ppm.
C35H41BF4NOPRu·0.5 CH2Cl2 (753.0): calcd. C 56.62, H 5.62, N
1.86%; found C 56.73, H 5.80, N 2.26%.
(Carbonyl)(cyclopentadienyl)(2,2-dipentylheptanenitrile)(tri-
phenylphosphine)iron-tetrafluoroborate (9a): IR (KBr): ν˜ =
2261vw (CN), 1979 s (CO), 1055vs,br (BF4) cm–1. 1H NMR ([D6]ace-
tone, 270 MHz): δ = 0.84 (m, 9 H, CH2CH3), 0.94–1.40 (m, 24 H,
CH2), 5.07 (s, 5 H), 7.27–7.78 (m, 15 H) ppm. 31P NMR ([D6]acetone,
109.4 MHz): δ = 66.88 (s) ppm.
(Carbonyl(cyclopentadienyl)(2,2-dibutylhexanenitrile)(triphenyl-
phosphine)ruthenium-tetrafluoroborate (4b): Yield 164 mg (89%).
M.p. 148 °C (dec.). IR(KBr): ν˜ = 2264 vw (CN), 1979 s (CO), 1054
1
Carbonyl)(cyclopentadienyl)(2-butyl-2-propylhexanenitrile)(tri- vs,br (BF4) cm–1. H NMR ([D6]acetone, 270 MHz): δ = 0.85 (t, J =
phenylphosphine)iron-tetrafluoroborate (10a): Yield 151 mg
6.8 Hz, 9 H, CH3), 1.18–1.46 (m, 18 H, CH2), 5.41 (s, 5 H), 7.38–
(93%). M.p. 114 °C (dec.). IR (KBr). ν˜ = 2241 vw (CN), 1980 s (CO), 7.67 (m,15 H) ppm. 31P NMR ([D6]acetone, 109.4 MHz): δ = 49.68
1
1054 vs,br (BF4) cm–1. H NMR ([D6]acetone, 270 MHz): δ = 0.87,
(s) ppm. C38H47BF4NOPRu·CH2Cl2 (837.6): calcd. C 55.93, H 5.90,
0.89, 0.92, (t, J = 7.3 Hz, 9 H, CH2 CH3), 1.12–1.62 (m, 16 H, CH2), N 1.67%; found C 56.16,H 6.23, N 1.71%.
5.08 (d, J = 1.4 Hz, 5 H), 7.43–7.68 (m, 15 H). 31P NMR ([D6]acetone,
109.4 MHz): δ = 66.93 (s) ppm. C37H45BF4Fe NOP·0.5CH2Cl2
(735.9): calcd. C 61,21, H 6.30, N 1.90%; found C 60.56, H 6.78, N
1.90%.
(Carbonyl)(cyclopentadienyl)(2,2-dimetylpentanenitrile)(triphen-
ylphosphine)ruthenium-tetrafluoroborate (5b): Yield 132 mg
(86%). M.p. 115 °C (dec.). IR (KBr): ν˜ = 2281 vw (CN), 1975 s (CO),
1
1053 vs,br (BF4) cm –1. H NMR ([D6]acetone, 270 MHz): δ = 0.84
(Carbonyl)(cyclopentadienyl)(tridecanenitrile)(triphenylphos- (t, J = 7.1 Hz, 3 H, CH3,1.12, 1.13 (s, 6 H, CCH3), 1.07–1.32 (m, 4 H,
phine)iron-tetrafluoroborate (11a): Yield 151 mg (90 %). M.p.
CH2), 5.42 (s, 5 H), 7.38–7.65 (m, 15 H) ppm. 13C NMR ([D6]acetone,
131 °C(dec.). IR (KBr): ν˜ = 2282 vw (CN), 1980 s (CO), 1055 vs,br 100.5 MHz): δ = 13.84 (CH2CH3), 18.87 (CH2CH3), 25.39 (C(CH3)2),
(BF4) cm–1. 1H NMR ([D6]acetone, 270 MHz): δ = 0.86 (t, J = 7.1 Hz,
35.69 (C(CH3)2), 42.49 (CCH2), 87.65 (Cp), 129.87 (d, J = 10.7 Hz,m),
3 H, CH2CH3), 2,58 (t, J = 7.1 Hz, 2 H, NCCH2), 1.14–1.58 (m, 18 132,13 (s, p), 133.91 (s,o),134.03 (s, i), 133.61 (CN) ppm.
H, CH2), 5.05 (d, J = 1.4 Hz, 5 H), 7.49–7.65 (m, 15 H) ppm. 3 1 P NMR ([D6 ]acetone, 109.4 MHz): δ = 49.88 (s) ppm.
Z. Anorg. Allg. Chem. 2017, 1262–1268
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Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
C31H33BF4NOPRu·.0.5CH2Cl2 (696.9): calcd. C 54.29, H 4.92 N
2.01%; found C 54.04, H 5.15, N 2.06%.
Acknowledgements
Support by Department Chemie, Ludwig-Maximilians-Universität
München (Professor Thomas Carell), is gratefully acknowledged. We
thank Dr. Markus Müller (LMU) for valuable advice in preparing the
manuscript.
(Carbonyl)(cyclopentadienyl)(2,2-dimethylhexanenitrile)(triphen-
ylphosphine)ruthenium-tetrafluoroborate (6b): Yield 139 mg
(88%). M.p. 125 °C (dec.). IR (KBr): ν˜ = 22.84 vw (CN), 1983 s
1
(CO), 1055 vs,br (BF4) cm –1. H NMR ([D6]acetone, 270 MHz): δ =
0.84 (t, J = 7.1 Hz, 3 H, CH3), 1.13, 1.14 (s, 6 H, CCH3), 1.06–1.27
(m, 6 H, CH2), 5.41 (s, 5 H), 7.38–7.77 (m, 15 H) ppm. 31P
N M R ( [ D 6 ] a c e t o n e , 1 0 9 . 4 M H z ) : δ = 4 9 . 9 7 ( s ) p p m .
C32H35BF4NOPRu·0.5CH2Cl2 (711.0): calcd. 54.91, H 5.10, N 1.97%;
found C 54.75, H 5.18, N 2.17%.
Keywords: Tertiary nitriles; Chiral carbonyl-cyclopenta-
dienyl-nitrile-triphenylphosphine iron and ruthenium com-
plexes / Iron; Ruthenium
(Carbonyl)(cyclopentadienyl)(tridecanenitrile)(triphenylphos-
phine)ruthenium-tetrafluoroborate (11b): Oily product. IR (KBr):
ν˜ = 2293 vw (CN), 1982 s (CO), 1056 vs,br (BF4) cm–1. 1H NMR
([D6]acetone, 270 MHz): δ = 0.84 (t, J = 7.1 Hz, 3 H, CH3), 1.14–1.23
(m, 16 H, CH2), 2.61 (m, 2 H, NCCH2), 5.35 (s, 5 H), 7.46–7.59 (m,
15 H) ppm. 13C NMR ([D6]acetone, 100.5 MHz): δ = 14.20 (CH3),
19.22 (NCCH2), 23.11, 25.10, 32.40 (CH2), 87.66 (Cp), 129.83 (d, J
= 10.7 Hz,m), 132.01 (d, J = 2, p), 133.43 (d, J = 49.0 Hz, i), 134.05
(d, J = 12.1 Hz,o), 133.86 (CN), 201,71 (d, J = 0.2 Hz, CO) ppm. 31P
NMR ([D6]acetone, 109.4 MHz): δ = 50.14 (s) ppm.
References
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Crystal Structure Determination of Complex 4b: A yellowish-
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Table 1
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Table 1. Experimental details for the structure determination of 4b.
4b
Empirical formula
Formula weight
Temperature /K
Crystal system
Space group
C38H47BF4NOPRu
752.61
293(2)
monoclinic
P21/c
a /Å
10.062(4)
b /Å
18.740(9)
c /Å
22.136(10)
β
98.94(3)°.
4123(3)
Volume /Å3
Z
4
ρcalc /g·cm–3
1.212
0.464
μ /mm–1
θ range for data collection /°
Reflections measured
Rint
2.049 to 20.045
4248
0.0747
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Observed reflections
Absorption correction
Max. and min. transmission
Parameters/restraints
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
S
3872
Empirical (SHELXA)
0.8191 and 0.3171
284/21
R1 = 0.1020, wR2 = 0.2613
R1 = 0.1727, wR2 = 0.3130
1.018
1.127
–0.556
no 1574068
Max electron density /e·Å–3
Min electron density /e·Å–3
CCDC
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Journal of Inorganic and General Chemistry
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Zeitschrift für anorganische und allgemeine Chemie
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Received: July 19, 2017
Published Online: October 9, 2017
Z. Anorg. Allg. Chem. 2017, 1262–1268
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© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim