Synthesis of substituted 1-acyl-1′-biphenylylferrocenes. Crystal structures of 4-bromo-4′-ferrocenylbiphenyl and 1-(4′-cyanobiphenyl- 4-yl)-1′-((S)-3-methylpentanoyl)ferrocene

Article abstract of DOI:10.1007/s11172-005-0053-6

Acylation of 4-bromo- and 4-cyano-4′-ferrocenylbiphenyl with alkanoyl chlorides afforded the corresponding 1-acyl-1′-biphenylylferrocenes in ～20% yields. X-ray diffraction study of the above-mentioned bromo derivative and 1-(4′-cyanobiphenyl-4-yl)-1′-((S)

Full text of DOI:10.1007/s11172-005-0053-6

1942
Russian Chemical Bulletin, International Edition, Vol. 53, No. 9, pp. 1942—1948, September, 2004
Synthesis of substituted 1ꢀacylꢀ1´ꢀbiphenylylferrocenes.
Crystal structures of 4ꢀbromoꢀ4´ꢀferrocenylbiphenyl and
1ꢀ(4´ꢀcyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀ((S)ꢀ3ꢀmethylpentanoyl)ferrocene
a
b
a
b
M. V. Makarov,aꢀ V. P. Dyadchenko, K. Yu. Suponitskii, D. A. Lemenovskii, and M. Yu. Antipin
ꢀ
aDepartment of Chemistry, Moscow State University,
Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (095) 939 0290. Eꢀmail: mihail_makarov@list.ru.
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085
Acylation of 4ꢀbromoꢀ and 4ꢀcyanoꢀ4´ꢀferrocenylbiphenyl with alkanoyl chlorides afꢀ
forded the corresponding 1ꢀacylꢀ1´ꢀbiphenylylferrocenes in ~20% yields. Xꢀray diffraction
study of the aboveꢀmentioned bromo derivative and 1ꢀ(4´ꢀcyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀ((S)ꢀ3ꢀ
methylpentanoyl)ferrocene demonstrated that these ferrocenylbiphenyl derivatives crystallize
in noncentrosymmetric space groups.
Key words: acylation, ferrocenylbiphenyls, Xꢀray diffraction study, nonlinear optics.
Ferroceneꢀcontaining derivatives that belong to maꢀ
chargeꢀtransfer system favorable for the manifestation of
nonlinear optical effects. The biphenyl moiety and the
cyclopentadienyl ring bound thereto impart a rodꢀlike
shape to the molecule, and the substituent X can contain a
flexible alkyl chain. Hence, compounds 1 can exhibit also
liquidꢀcrystalline properties provided that a rodꢀlike fragꢀ
ment is sufficiently long and the molecule is flexible. Acꢀ
tually, a number of ferrocenylꢀcontaining liquidꢀcrystalꢀ
line materials involve the biphenylyl group as the mesoꢀ
genic fragment, which is linked to the ferrocenyl moiety
either directly4 or through a spacer that provides flexibilꢀ
ity of the rigid conjugated system.5 Most studies were
devoted to the latter type of ferrocenylꢀcontaining mesoꢀ
gens, the carboxy group often serving as the spacer.6
4ꢀFerrocenylbiphenyl derivatives remain poorly studied.
Only one class of such compounds, viz., Schiff bases
Fc—C6H4—C6H4—CH=N—C6H4—OCnH2n+1 (n = 5,
8, 14), possessing liquidꢀcrystalline properties is known.4
Earlier,7 we have synthesized 4ꢀsubstituted 4´ꢀferꢀ
rocenylbiphenyls (including, compounds 2a and 3a;
Scheme 1) and studied the molecular and crystal strucꢀ
tures of these compounds. In the present study, we found
optimum conditions for the synthesis of compounds 1
containing the acyl group as the substituent X and estabꢀ
lished the structures of 4ꢀbromoꢀ4´ꢀferrocenylbiphenyl
and 1ꢀ(4´ꢀcyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀ((S)ꢀ3ꢀmethylpentaꢀ
noyl)ferrocene by Xꢀray diffraction analysis.
terials exhibiting nonlinear optical and liquidꢀcrystalline
properties have been extensively studied in recent years.1,2
These compounds have attracted attention due to both
specific properties of the ferrocenyl group (an easily poꢀ
larizable electron donor having a threeꢀdimensional sandꢀ
wich structure) and the fact that ferrocene derivatives are
more readily accessible than other organometallic comꢀ
pounds. The introduction of a ferrocenyl substituent into
a molecule of an organic compound can result in materiꢀ
als possessing new magnetic and electrochemical properꢀ
ties, which can be controlled by modifying the groups
bound to ferrocene and employing the ability of the latter
to undergo reversible redox transformations.2,3
With the aim of preparing such nonlinear optical and
liquidꢀcrystalline materials, we developed procedures for
the synthesis of compounds 1.
X = CnH2n+1CO, H; Q = Br, CN
Molecules 1 contain an electronꢀdonating (ferrocenyl)
group and an electronꢀwithdrawing (Q) group at the opꢀ
posite sides of the πꢀconjugated system giving rise to a
1ꢀAcylꢀ1´ꢀbiphenylylferrocenes can further be modiꢀ
fied and used as precursors for new liquidꢀcrystalline and
nonlinear optical materials.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1864—1870, September, 2004.
1066ꢀ5285/04/5309ꢀ1942 © 2004 Springer Science+Business Media, Inc.

1ꢀAcylꢀ1´ꢀbiphenylylferrocenes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
1943
Scheme 1
reagent ratio, and the reaction time on the yield of 1ꢀacylꢀ
1´ꢀbiphenylylferrocenes. The results of this investigation
are given in Table 1.
Acylation afforded a mixture of acyl derivatives conꢀ
taining also the starting ferrocenylbiphenyl. All acyl deꢀ
rivatives exhibit similar chromatographic mobilities on
Al2O3, which prevents their isolation and leads to losses
in the chromatography and crystallization. In all cases,
only heteroannularly substituted acylation products were
isolated. Their yields were, on the average, 20 %.
According to TLC data, acylation gave rise to heteroꢀ
annular isomers as the main products. This results is conꢀ
sistent with the fact that the biphenyl fragment bearing
the Br atom or the CN group exhibits electronꢀwithdrawꢀ
ing properties with respect to the ferrocenyl fragment and
deactivates the substituted C5H4 ring of ferrocenylbiphenyl
to a greater extent than the C5H5 ring. In 4ꢀferrocenylꢀ4´ꢀ
nitrobiphenyl (4), the nitro group completely inhibits the
reaction. The starting nitro compound was recovered in
54% yield due to partial decomposition in the course of
the reaction in boiling carbon disulfide.
Q = Br (2a), CN (3a),
Q = Br, R = nꢀC7H15 (2b), nꢀC10H21 (2c), nꢀC17H35 (2d),
Q = CN, R = Me (3b), nꢀC7H15 (3c),
Acylation was performed using carbon disulfide and
dichloromethane as the solvents. As can be seen from
Table 1, carbon disulfide has no advantages over dichloroꢀ
methane. The highest yield of 1ꢀacylꢀ1´ꢀbiphenylylꢀ
ferrocene was achieved in the reaction performed in the
presence of a twofold excess of AlCl3 for 13—15 h.
Study of compounds 2b—d and 3c,d demonstrated
that they do not form liquidꢀcrystalline phases in spite of
the presence of long alkyl chains. Presumably, the main
reason is the insufficient length of the rigid rodꢀlike fragꢀ
ment in the molecules of the compounds under considerꢀ
nꢀC10H21 (3d),
(3e)
Results and Discussion
Compounds 1 were synthesized by acylation of the
corresponding ferrocenylbiphenyls (see Scheme 1) taking
into account the known fact that arylation of substituted
ferrocenes gave unsatisfactory results.8
With the aim of searching for the optimum acylation
conditions, we examined the influence of the solvent, the
Table 1. Reaction conditions and results of acylation of ferrocenylbiphenyls 2a, 3a, and 4
Reaction conditions
Solvent
Reaction product
Ratio
t/h
Compound
Q
R
Yield
(%)
Fc(C6H4)2Q : RCOCl : AlCl3
1.0 : 1.0 : 1.4
1.0 : 1.0 : 1.4
1.0 : 1.0 : 1.6
1.0 : 1.1 : 2.0
1.0 : 1.0 : 1.6
1.0 : 1.1 : 2.0
1.0 : 1.0 : 1.4
1.0 : 1.1 : 2.0
1.0 : 1.1 : 2.0
CH2Cl2
CS2
CS2
CH2Cl2
CS2
CH2Cl2
CH2Cl2
CH2Cl2
CS2
20.5
2.5
5
22.5
2.5
15
5
14
4.5
2b
2b
2c
2c
2d
3b
3c
3d
3d
Br
Br
Br
Br
Br
CN
CN
CN
CN
C7H15
C7H15
C10H21
C10H21
C17H35
Me
C7H15
C10H21
C10H21
21a
26
17
27
17
22
10b
35
16c
1.0 : 1.1 : 2.0
1.0 : 1.0 : 1.7
CH2Cl2
CS2
13
3
3e
4а
CN
27
0d
NO2
C7H15
a The starting compound 2a was recovered in 17% yield.
b The starting compound 3a was recovered in 28% yield.
c The starting compound 3a was recovered in 18% yield.
d The starting 4ꢀferrocenylꢀ4´ꢀnitrobiphenyl (4) was recovered in 54% yield.

1944
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
Makarov et al.
ation, i.e., the ratio of the length of the biphenyl fragment
to the "thickness" of the ferrocene fragment is unfavorable
for stabilization of the mesophase.
a compound can be crystallized in a noncentrosymmetric
space group by varying the donor or acceptor substituents.9
Xꢀray diffraction data showed that compounds 2a
and 3e crystallize in the noncentrosymmetric space
groups P21 (2a) and P1 (3e).
The molecular structure of compound 3e is shown in
Fig. 1. The unit cell of acyl derivative 3e contains two
crystallographically independent molecules (A and B),
which are related by a pseudocenter of symmetry, except
for the substituents at the chiral carbon atom (Fig. 2). In
both molecules, the cyclopentadienyl rings of the ferꢀ
rocene moiety adopt a nearly eclipsed conformation. The
With the aim of searching for approaches to the conꢀ
struction of nonlinear optical materials (i.e., the materials
that crystallize in a noncentrosymmetric space group), we
studied the structures of compound 2a and chiral acyl
derivative 3e by Xꢀray diffraction analysis. It should be
noted that Xꢀray diffraction analysis of compounds 3a
and 4 has demonstrated7 that they crystallize in a cenꢀ
trosymmetric space group and, consequently, do not posꢀ
sess nonlinear optical activity. However, it is known that
C(21A)
C(23A)
C(22A)
N(1A)
C(15A)
C(16A)
C(20A)
C(14A)
C(17A)
C(4A)
C(5A)
C(1A)
C(3A)
C(2A)
C(13A)
C(18A)
C(19A)
C(11A)
C(12A)
Fe(1A)
C(9A)
C(8A)
C(7A)
C(28A)
C(25A)
C(26A)
C(29A)
C(24A)
C(10A)
C(6A)
O(1A)
C(27A)
Fig. 1. One of two crystallographically independent molecules (A) of compound 3e with displacement ellipsoids drawn at the
30% probability level.
c
0
a
Fe(1B)
C(6B)
C(9B)
C(10B)
C(10A)
C(9A)
C(6A)
Fe(1A)
b
Fig. 2. Fragment of the crystal packing of the 1ꢀ(4´ꢀcyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀ((S)ꢀ3ꢀmethylpentanoyl)ferrocene molecules.

1ꢀAcylꢀ1´ꢀbiphenylylferrocenes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
1945
C(10)—Cnt1—Cnt2—C(5) pseudotorsion angle is close
to 11° (Cnt1 and Cnt2 are the centroids of the Cp rings
bound to the acyl group and the biphenylꢀ4ꢀyl fragment,
respectively). The biphenyl fragment and the acyl group
are located at the same side of the ferrocene moiety, i.e.,
the molecule in the crystal adopts a Uꢀshaped conforꢀ
mation.
The Cp1—Ar1—Ar2 ring system (Ar = C6H4) is
nonplanar. The dihedral angles between the planes of the
Cp1 and Ar1 rings and the Ar1 and Ar2 rings are 10.6(6)°
and 40.2(3)°, respectively. All aromatic rings are planar
(the rms deviations are 0.001—0.013 Å). The rings of the
Cp1—Fe—Cp2 fragment are virtually coplanar. The angles
between the Cp1 and Cp2 planes are 1.8(8)° and 3.4(8)°
for the crystallographically independent molecules A
and B, respectively.
planes of the Cp1 and Ar1 rings and the Ar1 and Ar2
rings are 7.9(4)° and 18.7(2)° for the molecule A and
0.8(3)° and 14.2(3)° for the molecule B, respectively. The
C(10)—Cnt2—Cnt0—C(5) pseudotorsion angle (Cnt0 is
the centroid of the unsubstituted Cp ring) is 13° and 20°
in the molecules A and B, respectively. In the crystal of
compound 2a, the molecules A and B are also related by a
pseudocenter of symmetry and are arranged in a headꢀtoꢀ
tail fashion.
The crystal packing of the 4ꢀbromoꢀ4´ꢀferrocenylꢀ
biphenyl molecules (2a) is shown in Fig. 4. All intermoꢀ
lecular distances correspond to usual van der Waals conꢀ
tacts, except for the Br(1A)…H(5A´)—C(5A´) [1 – x,
–0.5 + y, 1 – z] contact characterized by the parameters
of 2.79 Å, 3.695(7) Å, and 153°. This contact occurs
between two molecules A.
Analysis of the crystal packing of molecules 3e showed
that all intermolecular distances in the crystal correspond
to usual van der Waals contacts. The adjacent planes of
the Cp rings, viz., C(6A)...C(10A) and C(6B)...C(10B),
of the ferrocenyl fragments of two independent molecules
are coplanar (the angle between these planes is 1.2(8)°)
(see Fig. 2). The shortest distances C(6A)...C(9B),
C(9A)...C(6B), and C(10A)...C(10B) are 3.649(14),
3.640(14), and 3.561(5) Å, respectively. The independent
molecules are related by a pseudocenter of symmetry and
are arranged in a headꢀtoꢀtail fashion due apparently to
dipoleꢀdipole interactions, with the resulting antiparallel
orientation of the dipole moments. This character of
the molecular packing is unfavorable for generation of
strong nonlinear optical effects because it leads to mutual
compensation of the contributions of molecular hyperꢀ
polarizability to the nonlinear optical susceptibility of the
crystal.
The bond lengths in molecules 2a and 3e have standard
values10 and correspond to the bond lengths in 4ꢀcyanoꢀ
4´ꢀferrocenylꢀ and 4ꢀferrocenylꢀ4´ꢀnitrobiphenyls 3a
and 4, which we have studied earlier.
Xꢀray diffraction study demonstrated that crystallizaꢀ
tion in a noncentrosymmetric space group can be achieved
by varying the substituent in compounds 1. The introducꢀ
tion of a chiral group having a particular configuration
necessarily results in a homochiral structure. One would
expect that this modification of the molecules not only
will allow one to prepare noncentrosymmetric crystals
but also will give rise to the optimum (from the viewpoint
of nonlinear optical activity) molecular packing.
Experimental
All experiments were carried out at 20 °C under argon using
the standard Schlenk technique. The compounds synthesized
were purified by column chromatography on Al2O3 (Brockmann
activity II). The course of the reactions was monitored by TLC
on Silufol plates. Anhydrous AlCl3 was purified by sublimaꢀ
tion in a vacuum of a waterꢀaspirator pump at 150—170 °C.
The crystal structure of compound 2a also contains
two independent molecules A (Fig. 3) and B, which
differ only in the conformation of the Cp1—Ar1—Ar2
and Cp1/Cp2 ring systems. The angles between the
C(22A)
Br(1A)
C(6A)
C(21A)
C(15A)
C(16A)
C(11A)
C(7A)
C(17A)
C(20A)
C(19A)
C(14A)
C(10A)
C(9A)
C(8A)
C(13A)
C(12A)
C(18A)
Fe(1A)
C(1A)
C(2A)
C(3A)
C(5A)
C(4A)
Fig. 3. One of the crystallographically independent molecules (A) of compound 2a with displacement ellipsoids drawn at the
30% probability level.

1946
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
c
Makarov et al.
0
b
C(20A)
H(5A´)
C(5A´)
Br(1A)
a
Fig. 4. Fragment of the crystal packing of the 4ꢀbromoꢀ4´ꢀferrocenylbiphenyl molecules.
Dichloromethane was distilled over CaH2. Carbon disulfide was
kept over P2O5 and distilled.
The H NMR spectra were recorded on a Varian VXRꢀ400
spectrometer (400 MHz) in CDCl3.
described above. The yield of compound 2b was 0.14 g (26%),
m.p. 130—133 °C.
1
1ꢀ(4´ꢀBromobiphenylꢀ4ꢀyl)ꢀ1´ꢀundecanoylferrocene (2c).
A. A mixture of AlCl3 (0.18 g, 1.35 mmol), undecanoyl chloride
(0.17 g, 0.84 mmol), and CS2 (7 mL) was stirred for 15 min, and
a solution of compound 2a (0.35 g, 0.84 mmol) in CS2 (15 mL)
was added. The reaction mixture was stirred for 5 h and then
worked up as described for 2b. The acylation product was
chromatographed on Al2O3. The starting compound 2a was
eluted with a 1 : 1 benzene—light petroleum mixture. Comꢀ
pound 2c was eluted with a 3 : 2 benzene—light petroleum
mixture and twice recrystallized from light petroleum (70/100).
Compound 2c was isolated in a yield of 0.085 g (17%) as paleꢀ
red crystals, m.p. 127—130 °C. Found (%): C, 67.86; H, 6.24.
1ꢀ(4´ꢀBromobiphenylꢀ4ꢀyl)ꢀ1´ꢀoctanoylferrocene (2b).
A. A mixture of aluminum chloride (0.19 g, 1.4 mmol), diꢀ
chloromethane (35 mL), and octanoyl chloride (0.17 mL, 0.16 g,
1 mmol) was stirred for 3.5 h until AlCl3 nearly completely
dissolved. The resulting solution of the acylating reagent was
added dropwise to a stirred solution of compound 2a (0.42 g,
1 mmol) in CH2Cl2 (15 mL) for 2 h. The reaction mixture was
stirred for 3.5 h, kept without stirring for 15 h, and poured
onto ice. Then concentrated HCl (8 mL) and CHCl3 (20 mL)
were added. The organic layer was separated, washed with water
to the neutral reaction, dried with MgSO4, and filtered. The
solvent was removed in vacuo and the residue was chromatoꢀ
graphed on Al2O3. The starting compound 2a was eluted with a
1 : 2 benzene—light petroleum mixture in a yield of 0.07 g
(17%). Crude product 2b was eluted in a yield of 0.15 g with
a 3 : 1 benzene—light petroleum mixture. Then the crude prodꢀ
uct was twice recrystallized from light petroleum (70/100). The
yield of 1´ꢀ(4´ꢀbromobiphenylꢀ4ꢀyl)ꢀ1ꢀoctanoylferrocene (2b)
was 0.12 g (21%), m.p. 132—134 °C. Found (%): C, 66.41;
H, 5.95; Fe, 10.16. C30H31BrFeO. Calculated (%): C, 66.32;
H, 5.75; Fe, 10.28. 1H NMR, δ: 0.88 (t, 3 H, Me); 1.26 (m,
8 H); 1.57 (m, 2 H, CH2CH2CO); 2.38 (t, 2 H, CH2CO); 4.37
(m, 4 H); 4.65 and 4.68 (both m, 2 H each); 7.44—7.57 (m, 8 H,
C6H4—C6H4).
1
C33H37BrFeO. Calculated (%): C, 67.71; H, 6.37. H NMR, δ:
0.87 (t, 3 H, CH3); 1.22 (m, 14 H); 1.51 (m, 2 H, CH2CH2CO);
2.39 (t, 2 H, CH2CO); 4.36 (m, 4 H), 4.64 and 4.68 (both m,
2 H each); 7.46—7.52 (m, 6 H, Ar); 7.55—7.57 (m, 2 H, Ar).
B. A mixture of AlCl3 (0.32 g, 2.4 mmol), undecanoyl chloꢀ
ride (0.27 g, 1.3 mmol), and CH2Cl2 (8 mL) was stirred for
20 min. Then a solution of compound 2a (0.50 g, 1.2 mmol) in
CH2Cl2 (23 mL) was added. The reaction mixture was stirred
for 8.5 h and then kept without stirring for 14 h. Compound 2c
was isolated by column chromatography on Al2O3 and recrystalꢀ
lized from light petroleum (70/100). The yield was 0.19 g (27%),
m.p. 127—130 °C.
1ꢀ(4´ꢀBromobiphenylꢀ4ꢀyl)ꢀ1´ꢀstearoylferrocene
(2d).
A mixture of compound 2a (0.40 g, 1 mmol), stearoyl chloride
(0.30 g, 1 mmol), and aluminum chloride (0.21 g, 1.6 mmol) in
carbon disulfide (20 mL) was stirred for 2.5 h. The reaction
mixture was worked up as described for 2b. The oily product was
chromatograped on Al2O3 using a 2 : 1 benzene—light petroꢀ
leum mixture as the eluent. After removal of the solvent, the
B. A mixture of AlCl3 (0.19 g, 1.4 mmol), octanoyl chloride
(0.17 mL, 0.16 g, 1 mmol), and carbon disulfide (18 mL) was
stirred for 1 h and then a solution of compound 2a (0.40 g,
1 mmol) in CS2 (7 mL) was added. The darkꢀcherry reaction
mixture was stirred for 2.5 h. Compound 2b was isolated as

1ꢀAcylꢀ1´ꢀbiphenylylferrocenes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
1947
residue (0.28 g) was recrystallized from light petroleum. The
yield of compound 2d was 0.11 g (17%), m.p. 111—113 °C.
Found (%): C, 70.32; H, 7.63; Br, 12.02. C40H51BrFeO. Calcuꢀ
lated (%): C, 70.28; H, 7.52; Br, 11.69. 1H NMR, δ: 0.88 (t, 3 H,
Me); 1.26 (m, 28 H); 1.57 (m, 2 H, CH2CH2CO); 2.38 (t, 2 H,
CH2CO); 4.37 (m, 4 H); 4.65 and 4.68 (both m, 2 H each);
7.44—7.57 (m, 8 H, C6H4—C6H4).
1ꢀAcetylꢀ1´ꢀ(4´ꢀcyanobiphenylꢀ4ꢀyl)ferrocene (3b). Alumiꢀ
num chloride (0.40 g, 3.0 mmol) was added to a solution of
acetyl chloride (0.13 g, 1.7 mmol) in CH2Cl2 (7 mL). The reacꢀ
tion mixture was stirred for 35 min. Then a solution of comꢀ
pound 3a (0.55 g, 1.5 mmol) in CH2Cl2 (20 mL) was added. The
reaction mixture was stirred for 15 h and worked up as in the
synthesis of 2b. The crude product was twice chromatographed
on Al2O3 using a 1 : 1 light petroleum—CHCl3 mixture as the
eluent. The solvent was distilled off and the residue was twice
recrystallized from a CH2Cl2—hexane mixture. Compound 3b
was isolated in a yield of 0.14 g (22%) as darkꢀred crystals,
m.p. 162—164 °C. Found (%): C, 74.25; H, 4.88; N, 3.38.
C25H19FeNO. Calculated (%): C, 74.09; H, 4.72; N, 3.46.
1H NMR, δ: 2.13 (s, 3 H, Me); 4.37, 4.39, 4.62, and 4.69 (all m,
2 H each); 7.50—7.56 and 7.70 (both m, 4 H each, C6H4).
1ꢀ(4´ꢀCyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀoctanoylferrocene (3c). A mixꢀ
ture of aluminum chloride (0.18 g, 1.4 mmol), dichloromethane
(20 mL), and octanoyl chloride (0.17 mL, 0.16 g, 1 mmol) was
stirred for 1.5 h. The resulting solution of the acylating reagent
was added dropwise to a stirred solution of compound 3a (0.36 g,
1 mmol) in CH2Cl2 (20 mL) for 2 h. The reaction mixture was
stirred for 3 h and worked up as described for 2b. Chromatoꢀ
graphy in benzene gave the starting compound 3a in a yield of
0.10 g (28%) and then the acylation product. This was recrystalꢀ
lized from a mixture of light petroleum with a small amount of
benzene. Compound 3c was isolated in a yield of 0.05 g (10%) as
red crystals, m.p. 129—131 °C. Found (%): C, 76.35; H, 6.34;
N, 2.81. C31H31FeNO. Calculated (%): C, 76.08; H, 6.38;
N, 2.86. 1H NMR, δ: 0.84 (t, 3 H, Me, 3J = 6.4 Hz); 1.22
(m, 8 H); 1.51 (m, 2 H, CH2CH2CO); 2.38 (t, 2 H, CH2CO,
3J = 7.2 Hz); 4.36, 4.38, 4.63, and 4.68 (all m, 2 H each);
7.49—7.55 and 7.70 (both m, 4 H each, C6H4).
1ꢀ(4´ꢀCyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀundecanoylferrocene (3d).
A. Under the conditions of acylation of 3b, compound 3a (0.57 g,
1.6 mmol) was acylated with undecanoyl chloride (0.37 g,
1.8 mmol) in the presence of AlCl3 (0.43 g, 3.2 mmol) and
chromatographed on Al2O3. An admixture of the starting nitrile
Table 2. Crystallographic data and details of Xꢀray diffraction study for compounds 2a and 3e
Parameter
2a
3e
Molecular formula
Molecular weight
C
22H17FeBr
417.12
C29H27FeNO
461.37
Crystal system
Space group
Monoclinic
P21
Triclinic
P1
T/К
λ/Å
Z
293(2)
0.71073
4
120(2)
0.71073
2
a/Å
b/Å
c/Å
α/deg
11.014(2)
7.6230(15)
20.781(4)
90
94.19(3)
90
5.9327(10)
12.379(2)
16.601(3)
105.984(4)
98.529(4)
102.194(4)
1117.6(3)
1.371
β/deg
γ/deg
V/Å3
1740.1(6)
1.592
dcalc/g cm–3
Absorption
3.162
0.697
coefficient µ/mm–1
F(000)
840
θ/2θ
2—27
7624
5538
484
ω (0.3° step)
2—29
10300
9430
0.0316
SADABS11
0.631/0.962
577
Scanning mode
θ Scan range/deg
Number of measured reflections
Number of independent reflections
Rint
Absorption correction
Tmin/Tmax
0.0233
ψ Scan
0.627/0.964
433
Number of parameters in refinement
GOOF
0.925
0.943
Number of reflections with I ≥ 2σ(I )
Convergence of refinement based on
reflections with I ≥ 2σ(I )
Convergence of refinement based
on all reflections
Flack parameter
3487
R1 = 0.0299
5180
R1 = 0.0578
wR2 = 0.0651
wR2 = 0.1093
0.099(9)
0.05(3)

1948
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 9, September, 2004
Makarov et al.
3a was eluted with a 3 : 1 light petroleum—Et2O mixture. Comꢀ
pound 3d was eluted with a 2 : 1 light petroleum—Et2O mixꢀ
ture and recrystallized first from a mixture of light petroleum
(70/100) with a small amount of benzene and then from an
acetone—hexane mixture. Compound 3d was isolated in a yield
of 0.29 g (35%) as red needleꢀlike crystals, m.p. 120—122 °C.
Found (%): C, 76.91; H, 6.94; N, 2.87. C34H37FeNO. Calꢀ
culated (%): C, 76.83; H, 7.02; N, 2.63. 1H NMR, δ: 0.86
(t, 3 H, CH3, 3J = 6 Hz); 1.21 (m, 14 H); 1.50 (m, 2 H,
CH2CH2CO); 2.38 (t, 2 H, CH2CO, 3J = 8 Hz); 4.36, 4.38,
4.63, and 4.68 (all m, 2 H each); 7.49—7.55 and 7.68—7.73
(both m, 4 H each, C6H4).
spectively. The crystallographic data and details of Xꢀray difꢀ
fraction study for compounds 2a and 3e are given in Table 2.
The structures of 2a and 3e were solved by direct methods
and refined by the fullꢀmatrix leastꢀsquares method with anisoꢀ
tropic thermal parameters against F 2hkl. The Xꢀray diffraction
data for the crystals of compound 3e were processed with the use
of the SAINT program.12 The final refinement was carried out
by the fullꢀmatrix leastꢀsquares method with anisotropic therꢀ
mal parameters. The coordinates of the hydrogen atoms were
calculated geometrically and refined using the riding model.
All calculations were carried out using the SHELXTL proꢀ
gram package13 on an IBM PC.
B. A mixture of AlCl3 (0.40 g, 3.0 mmol), undecanoyl chloꢀ
ride (0.34 g, 1.7 mmol), and carbon disulfide (8 mL) was stirred
for 20 min. Then a solution of nitrile 3a (0.55 g, 1.5 mmol) in
CS2 (40 mL) was added. The reaction mixture was stirred for
4.5 h and quenched by pouring onto a mixture of ice and conꢀ
centrated HCl as described for compound 2b. Chromatography
of the acylation product afforded the starting nitrile 3a in a yield
of 0.10 g (18%) and compound 3d. The latter was recrystallized
first from a mixture of light petroleum (70/100) with a small
amount of benzene and then from an acetone—hexane mixture.
The yield of compound 3d was 0.13 g (16%), m.p. 120—122 °C.
1ꢀ(4´ꢀCyanobiphenylꢀ4ꢀyl)ꢀ1´ꢀ((S)ꢀ3ꢀmethylpentanoyl)ferroꢀ
cene (3e). (S)ꢀ3ꢀMethylpentanoyl chloride (0.34 g, 2.5 mmol)
was added to a suspension of aluminum chloride (0.60 g,
4.5 mmol) in dichloromethane (10 mL). The reaction mixture
was stirred for 1 h. Then a solution of compound 3a (0.84 g,
2.3 mmol) in dichloromethane (30 mL) was added. The darkꢀ
cherry reaction mixture was stirred for 13 h. The oily product
was twice chromatographed on Al2O3 using a 1 : 1 hexꢀ
ane—CH2Cl2 mixture as the eluent. The product thus obtained
was twice recrystallized from a mixture of light petroleum
(70/100) with a small amount of benzene. Compound 3e was
isolated in a yield of 0.25 g (27%) as red needleꢀlike crystals,
m.p. 88—90 °C. Found (%): C, 75.44; H, 6.18; N, 3.01.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 03ꢀ03ꢀ
32840a).
References
1. C. Imrie, P. Engelbrecht, C. Loubser, and C. W. McCleland,
Appl. Organomet. Chem., 2001, 15, 1.
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E. Manoury, J. A. Delaire, I. MalteyꢀFanton, K. Nakatani,
and S. Di Bella, Organometallics, 1999, 18, 21.
3. R. Deschenaux, M. Schweissguth, M. T. Vilches, A. M.
Levelut, D. Hautot, G. J. Long, and D. Luneau, Organoꢀ
metallics, 1999, 18, 5553.
4. C. Imrie, P. Engelbrecht, C. Loubser, C. W. McCleland,
V. O. Nyamori, R. Bogardi, D. C. Levendis, N. Tolom,
J. van Rooyen, and N. Williams, J. Organomet. Chem., 2002,
645, 65.
5. C. Imrie, C. Loubser, P. Engelbrecht, C. W. McCleland,
and Y. Zheng, J. Organomet. Chem., 2003, 665, 48.
6. K. P. Reddy and T. L. Brown, Liq. Cryst., 1992, 12, 369.
7. D. A. Lemenovskii, M. V. Makarov, V. P. Dyadchenko,
A. E. Bruce, M. R. M. Bruce, S. A. Larkin, B. B. Averkiev,
Z. A. Starikova, and M. Yu. Antipin, Izv. Akad. Nauk, Ser.
Khim., 2003, 583 [Russ. Chem. Bull., Int. Ed., 2003, 52, 607].
8. A. N. Nesmeyanov, E. G. Perevalova, N. A. Simukova,
T. V. Nikitina, and P. D. Reshetov, Izv. Akad. Nauk SSSR,
Ser. Khim., 1961, 77 [Bull. Acad. Sci. USSR, Div. Chem. 1961
(Engl. Transl.))].
9. J. Bernstein, Polymorphism in Molecular Crystals, Oxford Uniꢀ
versity Press Inc., New York, 2002.
10. F. H. Allen, O. Kennard, D. Watson, L. Brammer, A. G.
Orpen, and R. Taylor, J. Chem. Soc., Perkin Trans. 2,
1987, S1.
11. G. M. Sheldrick, SADABS, Program for Empirical Absorption
Correction of Area Detector Data, University of Göttingen,
Göttingen (Germany), 1996.
12. SMART V5.051 and SAINT V5.00, Area Detector Control and
Integration Software, Bruker AXS Inc., Madison (WIꢀ53719,
USA), 1998.
C
29H27FeNO. Calculated (%): C, 75.50; H, 5.90; N, 3.04.
1H NMR, δ: 0.84 (t, 3 H, Me, 3J = 8 Hz); 0.87 (d, 3 H, Me, 3J =
8 Hz); 1.17, 1.32, 1.91, 2.24, and 2.42 (all m, 1 H each); 4.36
and 4.38 (both m, 2 H each); 4.61 and 4.63 (both m, 1 H each);
4.68 (m, 2 H); 7.50—7.55 and 7.67—7.73 (both m, 4 H each).
Reaction of 4ꢀferrocenylꢀ4´ꢀnitrobiphenyl with octanoyl chloꢀ
ride in the presence of AlCl3. Octanoyl chloride (0.06 mL,
0.3 mmol) was added to a suspension of aluminum chloride
(0.07 g, 0.5 mmol) in CS2 (10 mL). The reaction mixture was
stirred for 1 h. Then a solution of 4´ꢀferrocenylꢀ4ꢀnitrobipheꢀ
nyl (4) (0.13 g, 0.3 mmol) in CS2 (25 mL) was added. The
reaction mixture was stirred at 20 °C for 2 h, refluxed with
stirring for 1 h, and then worked up as described for comꢀ
pound 2b. Column chromatography on Al2O3 (benzene—light
petroleum, 2 : 1) yielded 0.07 g (54%) of 4ꢀferrocenylꢀ4´ꢀnitroꢀ
biphenyl (4).
Xꢀray diffraction study. Crystals of 1ꢀ(4´ꢀcyanobiphenylꢀ
4ꢀyl)ꢀ1´ꢀ((S)ꢀ3ꢀmethylpentanoyl)ferrocene (3e) suitable for
Xꢀray diffraction analysis were grown by gradual addition of
hexane to a solution of 3e in toluene. Crystals of 4ꢀbromoꢀ4´ꢀ
ferrocenylbiphenyl (2a) were grown analogously from a benꢀ
zene—hexane mixture. Xꢀray diffraction data for compounds 2a
and 3e were collected on a fourꢀcircle automated Siemens P3/PC
diffractometer and a SMART CCD 1000 diffractometer, reꢀ
13. G. M. Sheldrick, SHELXTLꢀ97, V5.10, Bruker AXS Inc.,
Madison (WIꢀ53719, USA), 1997.
Received July 2, 2004;
in revised form August 10, 2004