Synthesis, characterization and electrochemical properties of novel trinuclear ferrocenyl based organosilane compounds

Article abstract of DOI:10.1016/j.jorganchem.2014.02.001

Some trinuclear ferrocenyl based organosilane compounds were synthesized by hydrosilylation reaction of [4-(ethylferrocenyl)butyl]dimethylsilane and (4-ferrocenylbutyl)dimethylsilane with bisalkenylferrocene derivatives, in the presence of the Karstedt catalyst at room temperature. In addition a simple method for the preparation of 1,1′-bis(3-butenyl)alkylferrocenes from 1,1′-bis(4-chlorobutyl)alkylferrocenes under mild conditions was developed. ¹H and ¹³C NMR, FT-IR, GC-MS, CHN analysis, atomic absorbtion spectroscopy supported the predicted structure of the products. The electrochemical behavior of synthesized compounds was studied by cyclic voltammetry in CH₃CN/0.1 M LiClO₄ utilizing a glasse carbon working electrode. The relationship between the peak currents and the square root of the scan rate, showed that the redox process is diffusion limited.

Full text of DOI:10.1016/j.jorganchem.2014.02.001

Journal of Organometallic Chemistry 758 (2014) 36e44
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis, characterization and electrochemical properties of novel
trinuclear ferrocenyl based organosilane compounds
,
b
a,b
Reza Teimuri-Mofrad a , Kazem D. Safa , Keshvar Rahimpour
*
a Organic Synthesis Research Laboratory, Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz, 51664 Tabriz, Iran
b Organosilicon Research Laboratory, Department of Organic and Biochemistry, Faculty of Chemistry, University of Tabriz, 51664 Tabriz, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Some trinuclear ferrocenyl based organosilane compounds were synthesized by hydrosilylation reaction
of [4-(ethylferrocenyl)butyl]dimethylsilane and (4-ferrocenylbutyl)dimethylsilane with bisalkenylferro-
cene derivatives, in the presence of the Karstedt catalyst at room temperature. In addition a simple
method for the preparation of 1,10-bis(3-butenyl)alkylferrocenes from 1,10-bis(4-chlorobutyl)alkylferro-
cenes under mild conditions was developed. 1H and 13C NMR, FT-IR, GCeMS, CHN analysis, atomic
absorbtion spectroscopy supported the predicted structure of the products. The electrochemical behavior
of synthesized compounds was studied by cyclic voltammetry in CH3CN/0.1 M LiClO4 utilizing a glasse
carbon working electrode. The relationship between the peak currents and the square root of the scan
rate, showed that the redox process is diffusion limited.
Received 4 December 2013
Received in revised form
21 January 2014
Accepted 1 February 2014
Keywords:
Ferrocene
Bisalkenylferrocene
Hydrosilylation reaction
Cyclic voltammetry
Ó 2014 Elsevier B.V. All rights reserved.
1. Introduction
media, the accessibility of a large variety of derivatives, and its
favorable electrochemical properties have made ferrocenyl com-
Ferrocene as
a
historically important molecule was first
pounds very popular molecules for biological applications [25e28].
discovered in 1951, when Kealy and Pauson reacted cyclo-
pentadienyl magnesium bromide Grignard reagent with ferric
chloride [1,2], however its correct structure was only clarified soon
afterward independently by Wilkinson et al. [3] and Fischer and
Pfab [4]. The resemblance of its reactivity to that of benzene
inspired Woodward et al. to coin the new iron compound with the
name ferrocene [5]. The elucidation of its structure led to the birth
of the modern organometallic chemistry. Soon the scientific and
technical community got interested in ferrocene due to its fasci-
nating chemistry [6,7]. Chemists started to develop synthetic
strategies resulting ferrocene derivatives, and investigate their
applications in a wide range of scientific areas [8].
Due to the favorable electronic properties of ferrocene and its
easy functionalization, these compounds have found many appli-
cations in materials science, including electroactive materials [9e
11], catalysts [12e14], aerospace materials [15,16], medicines [17e
20], and sensors [21e23]. Recently ferrocene containing polymers
and molecules with several ferrocene units have attracted attention
with respect to their electrochemical, electronic and magnetic
properties [24]. The stability of ferrocene in aerobic and aqueous
Since the synthesis of the first silyl metal complex (
h
5-C5H5)
Fe(CO)2SiMe3 by Wilkinson in 1956, research transition metal silyl
compounds continues because these compounds are assumed to be
key intermediates in a number of important stoichiometric and
catalytic transformations [29,30]. Organosilicon reagents and
compounds are also valuable in organic synthesis. A special feature
of hydrosilanes is their ability to undergo hydrosilylation reaction
with different types of unsaturated compounds, like substituted
alkenes, leading to various organosilanes [31].
FriedeleCrafts acylation reactions are powerful tools for
substituting larger and more complex functional groups in place of
aromatic protons [32]. Similar to other aromatic compounds,
ferrocene is also incorporated in these reactions. Indeed, a lewis
acid e.g. aluminum chloride is needed as a catalyst. Alkylferrocenes
are obtained by a two step process involving the FriedeleCrafts
acylation of ferrocene continued by the reduction of the acylated
ferrocene [33]. Other methods like FriedeleCrafts alkylation re-
actions are also able to obtain this product, however the yield of
reaction would be reduced due to rearrangement in structure of the
formed carbocation.
Ferrocene derivatives are a well-known class of one-electron
donors which exhibit well established reversible redox couples.
As a consequence, ferrocene derivatives, particularly those pos-
sessing functionalized tethers, have emerged as strong candidates
* Corresponding author. Tel.: þ98 411 3393105; fax: þ98 411 3340191.
E-mail address: teymouri@tabrizu.ac.ir (R. Teimuri-Mofrad).
http://dx.doi.org/10.1016/j.jorganchem.2014.02.001
0022-328X/Ó 2014 Elsevier B.V. All rights reserved.

R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
37
Scheme 1. Synthesis of 1,10-bis(4-chlorobutyl) alkylferrocene.
for molecular electronic devices, electro-optical materials, multi-
electron redox catalysts and electrode surface modifiers [34,35].
Although there are several methods known for the formation of
vinyl or propenylferrocene, derivatives with longer alkenyl chains
are hardly known in literature. Previous methods for the synthesis
of alkenylferrocenes, were based on the dehydration and dehy-
drohalogenation reactions of corresponding ferrocenylalkanols
and ferrocenylalkylhalides with a suitable reagent, respectively
[36,37].
ferrocene derivatives we decided to use hydrosilylation reaction of
[4-(alkylferrocenyl)butyl]dimethylsilane and 1,10-bis(3-butenyl)
alkylferrocene derivatives for the synthesis of novel trinuclear
ferrocenyl based organosilane compounds.
Alkylferrocene derivatives like ethylferrocene (1b), pro-
pylferrocene (1c) and butylferrocene (1d) were synthesized ac-
cording to the modified procedure described by Graindorge and co-
workers in 89, 85 and 84% yields, respectively (Scheme 1) [33].
1,10-Bis(4-chlorobutyroyl)alkylferrocene derivatives were pre-
pared by FriedeleCrafts acylation of ferrocene and some alkylfer-
rocene derivatives (1ae1d) with two equivalent of 4-
chlorobutyroyl chloride in dichloromethane in the presence of
AlCl3 as catalyst (Scheme 1). 1,10-Bis(4-chlorobutyroyl) alkylferro-
cenes were reduced to the corresponding 1,10-bis(4-chlorobutyl)
alkylferrocenes (2ae2d) by NaBH4 in diglyme at 0 ꢀC in total yields
of 83e90% (Scheme 1).
Cyclic voltammetry (CV) has been widely used in investigating
the electrochemical properties of chemicals for its own advantages
[38]: ease of its operation, low cost and low dosage. While the
application of electrochemical methods in anion recognition re-
quires the receptor containing an electrochemical signaling unit,
the ferrocene group has been proven to be one of the most effective
electrochemical signaling units not only for its stable redox char-
acteristics, but also because it can significantly enhance its binding
strength with anion by modulating its own redox state [39e42].
To the best of our knowledge, there is no report available for the
synthesis of trinuclear ferrocenyl based organosilane derivatives
with (4-ferrocenylbutyl)dimethylsilyl group installed on both alkyl
groups of Cp rings of a center ferrocene matrix. In this article these
compounds have been designed and synthesized through hydro-
silylation reaction of 1,10-dialkenylferrocene and [4-(alkylferro-
The dehydrohalogenation of 1,10-bis(4-chlorobutyl) alkylferro-
cenes (2ae2d) in the presence of sodium tert-butoxide as a strong
base in DMSO as solvent at 50 ꢀC results in the corresponding
1,10-bis(3-butenyl) alkylferrocenes (3ae3d) in 76e82% yields
(Scheme 2). 1-(3-Butenyl)- 10-(4-chlorobutyl) ferrocene (4) was
isolated from reaction mixture before completion of the reaction
and the dehydrohalogenation reaction was consecutively carried
out on this product and compound 3a was obtained (Scheme 2).
cenyl)butyl]dimethylsilane
derivatives.
The
1,10-
dialkenylalkylferrocene derivatives were synthesized from the
elimination reaction of corresponding 1,10-bis(4-chlolorobutyl)
alkylferrocene derivatives under mild conditions using sodium
tert-butoxide as strong base. Furthermore, the electrochemical
properties of these novel compounds in solution were also studied.
2. Results and discussion
We have recently reported the dehydrocoupling reaction of (4-
ferrocenylbutyl)dimethylsilane with some alcohols derivatives in
the presence of the Karstedt catalyst for synthesis of various fer-
rocenylsilyl ethers [43]. A few articles reporting the synthesis and
electrochemistry of ferrocene derivatives are found in the literature
[9e11,29e31]. Due to interesting properties of silane based
Scheme 2. Synthesis of 1,10-bis(3-butenyl) alkylferrocene.

38
R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
We also achieved this conversion using potassium hydroxide as
a simple base in the dehydrohalogenation reaction of 1,10-bis(4-
chlorobutyl) ferrocene (2a), but in this case the yield of 3a as the
desired product was decreased to 58% and 1-(4-hydroxybutyl)-10-
(3-butenyl) ferrocene (5) was formed as byproduct in 15% yield
(Scheme 2).
A few articles reporting the synthesis of (4-ferrocenylbutyl)
dimethylsilane (7a) are found in the literature [44e46]. [4-
(ethylferrocenyl)butyl]dimethylsilane (7b) was synthesized from
(4-chlorobutyl) ethylferrocene (6b) via a Grignard reaction in
THF in 91% yield [44e46]. (4-Chlorobutyroyl) ethylferrocene was
prepared by FriedeleCrafts acylation of ethylferrocene with 4-
chlorobutyroyl chloride in dichloromethane in the presence of
AlCl3 as catalyst (Scheme 3) [33,47]. (4-Chlorobutyroyl) ethyl-
ferrocene was reduced to (4-chlorobutyl) ethylferrocene (6b)
by sodium borohydride in diglyme in 96% total yield
(Scheme 3) [33].
Scheme 4. Synthesis of trinuclear ferrocenyl based organosilanes.
response of the ferrocenyl compounds in the range of 0.025e
0.25 V sꢁ1. As seen, the anodic and cathodic peak currents increased
with increasing the scan rate. The plots of the anodic and cathodic
currents versus the square root of scan rates (v1/2) show a linear
relationship (Fig 4). This behavior suggests that the redox process is
diffusion limited.
Both reduction and oxidative peak currents increase obviously
as Fc unit increases in the structure of compounds (Fig 5). The
elevation of the Fc unit is responsible for the increase of elec-
troactive substance and the charge generated in the reaction
became more and more leading to the increasing of the peak
currents. These compounds can be potentially used as new
electroactive materials for sensors and other electrochemical
systems due to their well reversible redox behavior and the
ability to tailor functional groups without affecting the electro-
chemical aspects.
The hydrosilylation reaction of 1,10-bis(3-butenyl) alkylferro-
cenes (3ae3d) with (4-ferrocenyl butyl)dimethylsilane (7a) and [4-
(ethylferrocenyl)butyl]dimethylsilane (7b) in the presence of cat-
alytic amount of the Karstedt catalyst was carried out in toluene at
room temperature (Scheme 4). FT-IR spectroscopy was utilized to
follow the progress of the reaction, by monitoring the loss of the
SieH absorption at 2110 cmꢁ1 (Fig 1), the reaction was completed in
24 h. The novel trinuclear ferrocenyl based organosilanes (8ae8h)
(Table 1) were isolated as air stable, dark orange viscous oils. In the
1H NMR spectra of (6ae6h), appearance of a triplet around 0.5 ppm
corresponding to CH2SiMe2 and complete disappearance of eCH]
CH2 peaks were confirmed showing the end of hydrosilylation re-
action (Fig 2).
Data obtained from the mass spectra, IR, 1H and 13C NMR spectra
and elemental analyses are fully consistent with the proposed
structures.
In order to compare the influence of the substituents on the
redox ability of Fe (II), we carried out electrochemical studies on the
synthesized ferrocene derivatives. CV experiments performed in
dry CH3CN/0.100 M LiClO4 exhibited reversible voltammetric
behavior for the ferrocenyl group in this compounds with
3. Conclusion
In summary, we report the design and synthesis of some tri-
nuclear ferrocenyl based organosilane compounds through the
reaction of [4-(ethylferrocenyl)butyl]dimethylsilane and (4-
ferrocenylbutyl)dimethylsilane with dialkenylferrocene de-
rivatives, in the presence of the Karstedt catalyst at room temper-
ature. In addition a simple method for the preparation of 1,10-bis(3-
butenyl)alkylferrocenes from 1,10-bis(4-chlorobutyl)alkylferro-
cenes under mild conditions was developed. Electrochemical
behavior of synthesized compounds with the increase of scan rate
was investigated. The relationship between the peak currents and
the square root of the scan rate, showed that the electrode pro-
cesses were diffusion controlled.
D
Ep ¼ Epa ꢁ Epc ꢂ 0.08 V at scan rates up to 0.25 V sꢁ1 (Table 2).
Cathodic and anodic peak current ratios measured for the de-
rivatives were in the range 0.99 < ipc/ipa < 1.07, and Ep values were
independent of the scan rate.
All of the compounds exhibit only one pair of well-defined redox
peak in CH3CN indicating the existence of only one kind of elec-
troactive center in this compounds which is corresponding to its
ferrocenyl group. Fig 3 shows an example of typical voltammo-
grams of the ferrocene compounds in CH3CN/0.100 M LiClO4. The
influences of the scan rate was studied on the voltammetric
Scheme 3. Synthesis of [4-(alkylferrocenyl)butyl]dimethylsilane derivatives.

R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
39
Fig. 1. Comparing the FT-IR spectra of a) (4-ferrocenylbutyl)dimethylsilane (7a) b) 1,10-bis [4-[[4-(dimethylsilyl)butyl]ferrocenyl]butyl]ferrocene (8a).
4. Experimental
respectively. The FT-IR spectra were recorded on a Bruker-Tensor
270 spectrophotometer as KBr disks or smears between salt
plates. The mass spectra obtained with a GC-Mass Agilent quad-
rupole mode 5973N instrument, operating at 70 eV. Elemental
analyses were carried out with an Elementor Vario EL. III instru-
ment. Iron analysis was performed by Analytikjene (novaa 400)
atomic absorption spectrophotometer.
Cyclic voltammetry measurements were performed on 1 mM
solutions of ferrocene derivatives in dry CH3CN/0.1 M LiClO4 using
potentiostat/galvanostat Autolab (PGASTAT 30) equipped with a
standard three-electrode cell. A 2-mm-diameter GC was used as the
working electrode. A silver/silver chloride (Ag/AgCl) electrode and
a platinum electrode were used as the reference and the counter
electrodes, respectively. All potentials in this study are reported
with respect to the Ag/AgCl.
4.1. Solvents and reagents
Chemicals were either prepared in our laboratory or purchased
from Merck, Fluka, Sigma, Aldrich and Yantai Suny Chem. Interna-
tional Co., Ltd. Commerical solid reagents were used without
further purification. Liquid reactants were distilled prior to use.
Solvents were dried and distilled prior to use according to standard
laboratory practices; water was doubly distilled. THF and diglyme
were dried by refluxing under argon over sodium wire and distilled
directly before use. Column chromatography was performed on
silicagel 60 (Merck, grain size 0.063e0.2 mm) with n-hexane as
eluant. All reactions were carried out under an atmosphere of argon
in oven-dried glassware with magnetic stirring.
4.3. General procedure for the synthesis of alkylferrocene
4.2. Instrumentation
The 1H and 13C NMR spectra were recorded using a Bruker FT-
400 MHz spectrometer at room temperature and with CDCl3 as
solvent while chemical shifts are presented delta-values expressed
in ppm referenced to CHCl3 residue at 7.25 and 78 ppm,
A solution of acid chloride (63 mmol) in 30 ml dry dichloro-
methane was added to a suspension of anhydrous aluminum
chloride (8.41 g, 63 mmol) in 30 ml dry dichloromethane and the
mixture was stirred at 5 ꢀC for 1 h under Argon. The solution of
aluminum chloride: acid chloride complex was added dropwise
over 30 min to a solution of ferrocene (11.16 g, 60 mmol) in 100 ml
dry dichloromethane at 0 ꢀC. The reaction mixture was warmed to
room temperature and stirred for 16 h. A solution of NaBH4
(2.38 g, 63 mmol) in 25 ml diglyme was added dropwise to the
purple reaction mixture at ꢁ5 ꢀC. An orange solution was formed
and stirred at 0 ꢀC for 1 h. The mixture was then hydrolyzed with
addition of 20 ml water while maintaining its temperature at less
than or equal to 10 ꢀC. The mixture was allowed to separate by
settling and the organic phase was then withdrawn. The aqueous
phase was extracted with 3 times 30 ml of dichloromethane and
then all the organic phases are combined. Combined organic layer
was washed with 50 ml of brine and then dichloromethane was
distilled under atmospheric pressure. The diglyme and the resid-
ual ferrocene which was found to be entrained by the diglyme
were then distilled at reduced pressure approximately 20 mm Hg
and a column head temperature of 85ꢀe95 ꢀC. The alkylferrocene
derivatives were distilled at a more reduced pressure, less than
5 mm Hg.
Table 1
Synthesis of trinuclear ferrocenyl based organosilanes.
Entry
R1
R2
Product
Yield
1
2
3
4
5
6
7
8
H
H
H
H
Et
Et
Et
Et
H
8a
8b
8c
8d
8e
8f
68%
63%
59%
57%
64%
62%
56%
65%
Et
Pr
Bu
H
Et
Pr
Bu
8g
8h

40
R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
Fig. 2. NMR spectra of a) 1,10-bis(3-butenyl)ferrocene (3a) b) 1,10-bis [4-[[4-(dimethylsilyl)butyl]ferrocenyl]butyl]ferrocene (8a).
4.3.1. Ethylferrocene (1b)
stirred at room temperature for 1 h under Argon. The homogeneous
yellow solution was added dropwise to a solution of ferrocene or
alkylferrocene derivatives (54 mmol) in 130 ml dry dichloro-
methane at 0 ꢀC. The dark purple solution was then slowly allowed
to warm to room temperature. After 24 h stirring at room tem-
perature, a solution of NaBH4 (4.09 g, 108 mmol) in 50 ml diglyme
was added, while maintaining the temperature at less than or equal
to 0 ꢀC to the reaction mixture. A dark orange solution was formed
and stirred at 0 ꢀC for 1 h. The mixture was then hydrolyzed with
the addition of 120 ml water while maintaining its temperature at
less than or equal to 5 ꢀC. The mixture was allowed to separate by
settling and the organic phase was then withdrawn. The aqueous
phase was extracted with 3 times 50 ml of dichloromethane and
then all the organic phases were combined. Combined organic layer
was washed with 100 ml of brine and then dichloromethane was
distilled under atmospheric pressure. The diglyme were evaporated
under reduced pressure. The residue was purified by column
chromatography on silicagel with n-hexane as eluant. Specific de-
tails are given for each compound.
From 4.95 g acetylchloride, 11.43 g of light brown liquid was
obtained in 89% yield. 1H NMR (400 MHz, CDCl3, ppm): 1.16e1.19 (t,
3H, CH3), 2.32e2.37 (q, 2H, FcCH2), 3.99e4.16 (m, 9H, Fc); m/z (EI):
214 (100%[M]þ).
4.3.2. Propylferrocene (1c)
From 5.83 g propionylchloride, 11.63 g of light brown liquid was
obtained in 85% yield. 1H NMR (400 MHz, CDCl3, ppm): 0.93e0.96
(t, 3H, CH3), 1.49e1.58 (m, 2H, CH2CH3), 2.31e2.35 (t, 2H, FcCH2),
4.05e4.15 (m, 9H, Fc); m/z (EI): 228 (100%[M]þ).
4.3.3. Butylferrocene (1d)
From 6.71 g butyrylchloride, 12.20 g of light brown liquid was
obtained in 84% yield. 1H NMR (400 MHz, CDCl3, ppm): 0.89e0.92
(t, 3H, CH3), 1.31e1.36 (m, 2H, CH2CH3), 1.42e1.45 (m, 2H,
CH2CH2CH3), 2.29e2.36 (t, 2H, CpCH2), 4.02e4.13 (m, 9H, Fc); m/z
(EI): 242 (100%[M]þ).
4.4. General procedure for the synthesis of 1,10-bis(4-chlorobutyl)
alkylferrocene
4.4.1. 1,10-Bis(4-chlorobutyl)ferrocene (2a)
From 10.04 g ferrocene, 17.63 g of orange liquid was obtained in
89% yield. FT-IR (KBr, cmꢁ1): 3084 (CpeH), 2938 (CeH), 1648, 1455
(C]C), 1312 (CH2eCl), 1025 (Cp), 815 (CeCl), 496 (CpeFe); 1H NMR
(400 MHz, CDCl3, ppm): 1.62e1.66 (m, 4H, CpCH2CH2), 1.76e1.82
(m, 4H, CH2CH2Cl), 2.33e2.37 (t, 4H, CpeCH2), 3.53e3.56 (t, 4H,
A solution of 4-chlorobutyroyl chloride (15.28 g, 108 mmol) in
50 ml dry dichloromethane was added dropwise at room temper-
ature to a suspension of anhydrous aluminum chloride (15.89 g,
119 mmol) in 50 ml of dry dichloromethane. The mixture was

R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
41
Table 2
Selected potentials (V) and current (
m
A) data for 1.0 mM solutions of the ferrocenyl
containing compounds in CH3CN/0.100 M LiClO4 at 25.0 ꢀC.
Compound
DEp
ipc/ipa
Compound
DEp
ipc/ipa
2a
2b
2c
2d
3a
3b
3c
3d
0.078
0.079
0.073
0.076
0.073
0.079
0.080
0.075
1.02
1.04
1.03
0.99
1.03
1.03
1.02
0.99
5a
5b
5c
5d
5e
5f
0.073
0.080
0.079
0.074
0.060
0.078
0.080
0.080
0.99
1.05
1.03
0.99
1.04
1.07
0.99
1.02
5g
5h
CH2Cl), 3.98 (d, 4H, J ¼ 1.4 Hz, CH2C5H4), 4.00 (d, 4H, J ¼ 1.4 Hz,
CH2C5H4); 13C NMR (100 MHz, CDCl3, ppm): 27.38 (CpCH2CH2),
27.61 (CH2CH2Cl), 31.28 (CpCH2), 43.97 (CH2Cl), 67.59, 66.83 (Cp),
87.42 (CpCH2); m/z (EI): 368 (64.26%[M]þ), 366 (100%[M]þ), 91
(14.82% [CH2CH2CH2CH2Cl]þ); Anal. Calc. for: C18H24Cl2Fe
(367.141): C, 58.89; H, 6.59; Fe, 15.21. Found: C, 58.86; H, 6.55; Fe,
15.11%.
Fig. 4. Linear relationship between the A) cathodic peak current, B) anodic peak
current and the square root of scan rates.
86.37 (CpCH2); m/z (EI): 410 (64.19%[M]þ), 408 (100%[M]þ), 91
(17.45% [CH2CH2CH2CH2Cl]þ); Anal. Calc. for: C21H30Cl2Fe (409.22):
C, 61.63; H, 7.38; Fe, 13.64. Found: C, 61.89; H, 7.34; Fe, 13.56%.
4.4.2. 1,10-Bis(4-chlorobutyl) ethylferrocene (2b)
From 11.56 g ethylferrocene, 18.34 g of orange liquid was ob-
tained in 86% yield. FT-IR (KBr, cmꢁ1): 3082 (CpeH), 2935 (CeH),
1675, 1449 (C]C), 1309 (CH2eCl), 1032 (Cp), 820 (CeCl), 496 (Cpe
Fe); 1H NMR (400 MHz, CDCl3, ppm): 1.12e1.16 (t, 3H, CH3), 1.57e
1.67 (m, 4H, CpCH2CH2), 1.76e1.81 (m, 4H, CH2CH2Cl), 2.26e2.36
4.4.4. 1,10-Bis(4-chlorobutyl) butylferrocene (2d)
From 13.07 g butylferrocene, 18.96 g of orange liquid was ob-
tained in 83% yield. FT-IR (KBr, cmꢁ1): 3082 (CpeH), 2933 (CeH),
1707, 1451 (C]C), 1305 (CH2eCl), 1034 (Cp), 819 (CeCl), 496 (Cp-
Fe); 1H NMR (400 MHz, CDCl3, ppm): 0.90e0.94 (t, 3H, CH3), 1.31e
1.37 (m, 2H, CH2CH2CH3), 1.43e1.48 (m, 2H, CH2CH3), 1.60e1.67 (m,
4H, CpCH2CH2), 1.78e1.82 (m, 4H, CH2CH2Cl), 2.25e2.36 (m, 6H,
CpCH2), 3.52e3.54 (t, 4H, CH2Cl), 3.86e3.94 (m, 7H, Cp); 13C NMR
(100 MHz, CDCl3, ppm): 12.97(CH3), 21.62 (CH2CH3), 27.61, 27.38,
26.89 (CH2), 31.50, 31.36, 31.28 (CpCH2), 43.96 (CH2Cl), 68.45, 67.52,
67.36, 67.21, 66.48 (Cp), 88.24, 87.15, 86.39 (CpCH2); m/z (EI): 424
(65.09%[M]þ), 422 (100%[M]þ), 91 (13.10% [CH2CH2CH2CH2Cl]þ);
Anal. Calc. for: C22H32Cl2Fe (423.243): C, 62.43; H, 7.62; Fe, 13.19.
Found: C, 62.10; H, 7.58; Fe, 13.11%.
(m, 6H, CpCH2), 3.52e3.54 (t, 4H, CH2Cl), 3.86e3.99 (m, 7H, Cp); 13
C
NMR (100 MHz, CDCl3, ppm): 12.56 (CH3), 27.38 (CpeCH2CH2),
27.59 (CH2CH2Cl), 31.49, 31.39, 31.30 (CpCH2), 43.94 (CH2Cl), 68.28,
67.38, 67.31, 67.13, 66.58 (Cp), 88.28, 86.14, 85.48 (CpCH2); m/z (EI):
396
(64.93%[M]þ),
394
(100%[M]þ),
91
(14.74%
[CH2CH2CH2CH2Cl]þ); Anal. Calc. for: C20H28Cl2Fe (395.195): C,
60.78; H, 7.14; Fe, 14.13. Found: C, 60.45; H, 7.10; Fe, 14.05%.
4.4.3. 1,10-Bis(4-chlorobutyl) propylferrocene (2c)
From 12.31 g propylferrocene, 19.88 g of orange liquid was ob-
tained in 90% yield. FT-IR (KBr, cmꢁ1): 3099 (CpeH), 2935 (CeH),
1675, 1449 (C]C), 1319 (CH2eCl), 1039 (Cp), 820 (CeCl), 497 (Cpe
Fe); 1H NMR (400 MHz, CDCl3, ppm): 0.90e0.93 (t, 3H, CH3), 1.44e
1.49 (m, 2H, CH2CH3), 1.59e1.66 (m, 4H, CpCH2CH2), 1.76e1.82 (m,
4H, CH2CH2Cl), 2.23e2.33 (m, 6H, CpCH2), 3.52e3.54 (t, 4H, CH2Cl),
3.85e3.93 (m, 7H, Cp); 13C NMR (100 MHz, CDCl3, ppm): 12.59
(CH3), 27.71, 27.60, 23.81 (eCH2e), 31.49, 31.38, 31.29 (CpCH2),
43.98 (CH2Cl), 68.48, 67.58, 67.34, 67.15, 66.68 (Cp), 88.26, 87.13,
4.5. General procedure for the synthesis of 1,10-bis(3-butenyl)
alkylferrocene
A 50 ml round-bottom flask was charged with 1,10-bis(4-
chlorobutyl) alkylferrocene (2.7 mmol), sodium tert-butoxide
(8.1 mmol) and 16 ml DMSO as solvent under argon. Mixture was
Fig. 5. CV curves for 1.0 mM of a) 1,10-bis(4-chlorobutyl)ferrocene b) 1,10-bis [4-[[4-
Fig. 3. CV curves of the 1,10-bis(4-chlorobutyl)ferrocene in different scan rates. (a)
(dimethylsilyl) butyl]ferrocene]butyl]ferrocene in CH3CN/0.100
M
LiClO4 at
0.025 (b) 0.05 (c) 0.1 (d) 0.15 (e) 0.2 (f) 0.25 V sꢁ1
.
250 mV sꢁ1
.

42
R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
stirred at 50 ꢀC and reaction progress was monitored with thin
layer chromatography (TLC) until complete disappearance of 1,10-
bis(4-chlorobutyl) alkylferrocene. The mixture was allowed to cool
to room temperature and extracted with 4 times 25 ml of n-hexane
and then all the n-hexane phases were combined. The combined n-
hexane extracts were washed with 3 times 10 ml water and dried
over Na2SO4 before removal of the solvent. The solvent was evap-
orated and the residue purified by column chromatography with n-
hexane as eluant to give the corresponding products. Specific de-
tails are given for each compound.
[M]þ); Anal. Calc. for: C22H30Fe (350.32): C, 75.43; H, 8.63; Fe, 15.94.
Found: C, 74.17; H, 8.58; Fe 15.85%.
4.5.5. 1-(3-Butenyl)-10-(4-chlorobutyl) ferrocene (4)
Orange oil. FT-IR (KBr, cmꢁ1): 3082 (CpeH), 2925 (CeH), 1640,
1620, 1452 (C]C), 1311 (CH2eCl), 1032 (Cp), 814 (CeCl), 494 (Cpe
Fe); 1H NMR (400 MHz, CDCl3, ppm): 1.63e1.69 (m, 2H,
CH2CH2CH2Cl), 1.77e1.82 (m, 2H, CH2CH2Cl), 2.23e2.31 (m, 2H,
CpCH2CH2CH]), 2.35e2.38 (t, 2H, CpCH2CH2CH2CH2Cl), 2.40e2.44
(t, 2H, CpCH2CH2CH]), 3.53e3.56 (t, 2H, CH2Cl), 3.99e4.01 (m, 8H,
Cp), 4.98 (d, J ¼ 10.1 Hz, 1H, ]CH2), 5.05 (d, J ¼ 17.1 Hz, 1H, ]CH2),
5.82e5.92 (m, 1H, eCH]); 13C NMR (100 MHz, CDCl3, ppm): 27.38
(CpCH2CH2CH2), 27.61 (CH2CH2Cl), 27.95 (CH2CH]), 31.28
(CpCH2CH2CH2), 34.43 (CpCH2CH2CH]), 43.90 (CH2Cl), 66.76,
4.5.1. 1,10-Bis(3-butenyl)ferrocene (3a)
From 0.99 g 1,10-bis(4-chlorobutyl)ferrocene, 0.63 g of orange oil
was obtained in 79% yield. FT-IR (KBr, cmꢁ1): 3083 (CpeH), 2930
(CeH), 1647, 1629, 1460 (C]C), 1025 (Cp), 503 (CpeFe); 1H NMR
(400 MHz, CDCl3, ppm): 2.23e2.28 (m, 4H, CpCH2CH2), 2.39e2.43
(t, 4H, CpCH2), 3.99e4.01 (m, 8H, Cp), 4.97 (d, J ¼ 10.1 Hz, 2H, ]
0
66.81, 67.33, 67.39 (Cp), 87.37 (C1 Cp), 87.53 (C1 Cp), 113.49 (]CH2),
137.50 (eCH]); m/z (EI): 332.5 (63.28%[M]þ), 330.5 (100%[M]þ);
Anal. Calc. for: C18H23ClFe (330.68): C, 65.38; H, 7.01; Fe, 16.89.
Found: C, 65.61; H, 6.97; Fe, 16.8%.
CH2), 5.03 (d, J ¼ 17.1 Hz, 2H, ]CH2), 5.82e5.89 (m, 2H, eCH]); 13
C
NMR (100 MHz, CDCl3, ppm): 27.95 (CpCH2CH2), 34.43 (CpCH2),
66.76, 67.60 (Cp), 87.56 (CpCH2), 113.50 (]CH2), 137.58 (eCH]); m/
z (EI): 294 (100%[M]þ), 199 (28.04% [FceCH2]þ); Anal. Calc. for:
4.5.6. 1-(4-Hydroxybutyl)-10-(3-butenyl) ferrocene (5)
Orange oil. FT-IR (KBr, cmꢁ1): 3480 (OeH), 3084 (CpeH), 2923
(CeH), 1642, 1622, 1451 (C]C), 1030 (Cp), 496 (CpeFe); 1H NMR
(400 MHz, CDCl3, ppm): 1.34e1.36 (br, 1H, OH), 1.52e1.62 (m, 4H,
CpCH2CH2CH2CH2OH), 2.23e2.29 (m, 2H, CpCH2CH2CH]), 2.33e
2.36 (t, 2H, CpCH2CH2CH2CH2OH), 2.39e2.43 (t, 2H,
CpCH2CH2CH]), 3.62e3.65 (t, 2H, CH2OH), 3.98e4.01 (m, 8H, Cp),
4.97 (d, J ¼ 10.1 Hz, 1H, ]CH2), 5.03 (d, J ¼ 17.1 Hz, 1H, ]CH2),
5.81e5.91 (m, 1H, eCH]); 13C NMR (100 MHz, CDCl3, ppm): 26.43
(CpCH2CH2CH2), 27.91 (CH2CH2OH), 28.19 (CH2CH]), 31.56
(CpCH2CH2CH2), 34.41 (CpCH2CH2CH]), 61.83 (CH2OH), 66.75,
C
18H22Fe (294.219): C, 73.48; H, 7.54; Fe, 18.98. Found: C, 73.05; H,
7.58; Fe, 18.87%.
4.5.2. 1,10-Bis(3-butenyl)ethylferrocene (3b)
From 1.07 g 1,10-bis(4-chlorobutyl) ethylferrocene, 0.71 g of or-
ange oil was obtained in 82% yield. FT-IR (KBr, cmꢁ1): 3076 (CpeH),
2923 (CeH), 1643, 1625, 1444 (C]C), 1056 (Cp), 494 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): 1.12e1.16 (t, 3H, CH3), 2.23e2.32 (m,
4H, CpCH2CH2), 2.35e2.43 (m, 6H, CpCH2), 3.88e3.99 (m, 7H, Cp),
4.96 (d, J ¼ 10.0 Hz, 2H, ]CH2), 5.03 (d, J ¼ 17.1 Hz, 2H, ]CH2),
5.82e5.87 (m, 2H, eCH]); 13C NMR (100 MHz, CDCl3, ppm): 13.73
(CH3), 26.44, 27.88 (CpCH2CH2), 34.21, 34.39, 34.65 (CpCH2), 66.57,
67.23, 67.56, 67.84, 68.29 (Cp), 86.78, 87.42, 89.35 (CpCH2), 113.38
(]CH2), 137.60 (eCH]); m/z (EI): 322 (100%[M]þ); Anal. Calc. for:
0
66.79, 67.58, 67.62 (Cp), 87.51 (C1 Cp), 87.80 (C1 Cp), 113.49 (]CH2),
137.58 (eCH]); m/z (EI): 312 (100%[M]þ); Anal. Calc. for:
C18H24OFe (312.235): C, 69.24; H, 7.75; Fe, 17.88. Found: C, 68.81; H,
7.8; Fe, 17.76%.
C
20H26Fe (322.26): C, 74.54; H, 8.13; Fe, 17.33. Found: C, 74.18; H,
4.6. Preparation of (4-chlorobutyl)alkylferrocene
8.08; Fe, 17.23%.
4.6.1. 4-Chlorobutylferrocene (6a)
6a was prepared according to procedure described by J.C.
Gautier and J.C. Mondet [47].
4.5.3. 1,10-Bis(3-butenyl)propylferrocene (3c)
From 1.1 g 1,10-bis(4-chlorobutyl) propylferrocene, 0.69 g of or-
ange oil was obtained in 76% yield. FT-IR (KBr, cmꢁ1): 3076 (CpeH),
2923 (CeH), 1641, 1620, 1449 (C]C), 1048 (Cp), 496 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): 0.91e0.94 (t, 3H, CH3), 1.48e1.51 (m,
2H, CH2CH3), 2.23e2.27 (m, 6H, CpCH2CH2, CpCH2CH2CH3), 2.36e
2.39 (t, 4H, CpCH2), 3.87e4.00 (m, 7H, Cp), 4.97 (d, J ¼ 9.7 Hz,
2H, ¼CH2), 5.03 (d, J ¼ 17.0 Hz, 2H, ¼CH2), 5.86e5.87 (m, 2H, e
CH]); 13C NMR (100 MHz, CDCl3, ppm): 13.21 (CH3), 22.05
(CH2CH3), 26.86, 28.01 (eCH2e), 30.65, 33.48, 34.64 (CpCH2), 66.57,
66.75, 66.86, 67.61, 68.33 (Cp), 85.66, 86.40, 87.40, (CpCH2), 113.37
(¼CH2), 137.63 (eCH]); m/z (EI): 336 (100%[M]þ); Anal. Calc. for:
4.6.2. 1-(4-Chlorobutyl)ethylferrocene (6b)
6b was prepared according to similar procedure as section 4.6.1.
as yellowish oil in 96% yield: FT-IR (KBr, cmꢁ1): 3088 (CpeH), 2931,
2860 (CeH), 1667, 1450 (C]C), 1311, 1227 (CH2eCl),1104,1038 (Cp),
824 (CeCl), 492 (CpeFe); 1H NMR (400 MHz, CDCl3, ppm): 1.12e
1.15 (t, 3H CH3), 1.54e1.67 (m, 2H, CpCH2CH2), 1.75e1.81 (m, 2H,
CH2CH2Cl), 2.25e2.39 (m, 4H, CpCH2), 3.55e3.56 (t, 2H, CH2Cl),
3.96e4.12 (m, 8H, Cp); 13C NMR (100 MHz, CDCl3, ppm): 12.54
(CH3), 27.38 (CpCH2CH2), 27.59 (CH2CH2Cl), 31.49, 31.36 (CpCH2),
43.96 (CH2Cl), 67.38, 67.31, 67.13, 66.58 (Cp), 88.28, 86.14 (CpCH2);
Anal. Calc. For: C16H21ClFe (304.64): C, 63.08; H, 6.95; Fe, 18.33.
Found: C, 63.32; H, 6.91; Fe, 18.22%.
C
21H28Fe (336.29): C, 75.00; H, 8.39; Fe, 16.61. Found: C, 74.60; H,
8.34; Fe, 16.52%.
4.5.4. 1,10-Bis(3-butenyl) butylferrocene (3d)
From 1.14 g 1,10-bis(4-chlorobutyl) butylferrocene, 0.74 g of or-
ange oil was obtained in 78% yield. FT-IR (KBr, cmꢁ1): 3076 (CpeH),
2924 (CeH), 1639, 1628, 1452 (C]C), 1045 (Cp), 495 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): 0.88e0.92 (t, 3H, CH3), 1.30e1.35 (m,
2H, CH2CH3), 1.43e1.45 (m, 2H, CH2CH2CH3), 2.22e2.26 (m, 6H,
CpCH2CH2,CpCH2), 2.34e2.39 (t, 4H, CpCH2), 3.85e4.06 (m, 7H, Cp),
4.96 (d, J ¼ 9.8 Hz, 2H, ]CH2), 5.03 (d, J ¼ 17.2 Hz, 2H, ]CH2), 5.83e
5.89 (m, 2H, eCH]); 13C NMR (100 MHz, CDCl3, ppm): 13.02 (CH3),
21.69 (eCH2CH3), 26.39, 27.85, 28.10 (CpCH2CH2), 30.37, 34.34,
34.64 (CpCH2), 66.55, 66.68, 67.60, 67.94, 68.31 (Cp), 86.80, 87.39,
87.74 (CpCH2), 113.45 (]CH2), 137.71 (eCH]); m/z (EI): 350 (100%
4.7. Preparation of [4-(alkylferrocenyl)butyl]dimethylsilane
4.7.1. (4-Ferrocenylbutyl)dimethylsilane (7a)
7a was prepared according to procedure described by M.
Immelman, J.C. Swarts, G.J. Lamprecht and S.E. Greyling [44].
4.7.2. [4-(Ethylferrocenyl)butyl]dimethylsilane (7b)
7b was prepared according to similar procedure as Section 4.7.1.
as dark brown oil in 91% yield: FT-IR (KBr, cmꢁ1): 3089 (CpeH),
2960 (CeH), 2110 (SieH), 1635, 1454 (Cp), 1250 (CeSi), 1031 (Cp),
491 (CpeFe); 1H NMR (400 MHz, CDCl3, ppm): 0.09e0.14 (d, 6H,

R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
43
Si(CH3)2), 0.61e0.65 (t, 2H, CH2Si(CH3)2), 0.91e0.96 (m, 2H,
CH2CH2Si(CH3)2), 1.16e1.21 (t, 3H, CH3), 1.43e1.56 (m, 2H, Cpe
CH2eCH2), 2.31e2.37 (m, 4H, CpeCH2), 3.97e4.05 (m, 9H, Cp, Sie
H); 13C NMR (100 MHz, CDCl3, ppm): ꢁ3.59 (Si(CH3)2), 13.26
(CH2CH3), 25.36 (CH2Si(CH3)2), 27.88, 28.49 (eCH2e), 31.56, 34.65
(CpCH2), 66.58, 67.13, 67.31, 67.38 (Cp), 86.14, 88.28 (CpCH2); Anal.
Calc. for: C18H28FeSi (328.347): C, 65.84; H, 8.59; Fe, 17.01. Found: C,
65.52; H, 8.55%; Fe, 17.12%.
Si(CH3)2), 13.23 (CH3), 21.26, 21.53 (CH2SiMe2), 23.89 (CH2eCH3),
27.60, 28.02 (eCH2e), 31.29, 32.49, 34.27, 34.64 (CpCH2), 65.57,
65.84, 66.43, 66.76, 67.13, 67.58, 67.61, 67.85 (Cp), 86.18, 87.42,
87.50, 88.26(CpCH2); Anal. Calc. for: C53H76Fe3Si2 (936.90): C, 67.95;
H, 8.18; Fe, 17.88. Found: C, 67.62; H, 8.14; Fe, 17.79%.
4.8.4. 1,10-Bis[4-[[4-(dimethylsilyl)butyl]ferrocenyl]butyl]
butylferrocene (8d)
From 0.35 g 3d and 0.60 g 6a, 0.52 g of dark orange oil was
obtained in 57% yield. FT-IR (KBr, cmꢁ1): 3088 (CpeH), 2925 (CeH),
1648, 1458 (C]C), 1254, 812 (CeSi), 1100 (Cp), 490 (CpeFe);1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.03 (s, 12H, Si(CH3)2), 0.49e0.53 (t,
8H, CH2SiMe2), 0.89e0.93 (t, 3H, CH3), 1.30e1.35 (m, 10H,
CpCH2CH2CH2), 1.45e1.55 (m, 10H, CpCH2CH2), 2.30e2.35 (t, 10H,
CpeCH2), 3.85e3.99 (m, 7H, C5H4, C5H3), 4.04e4.05 (d, 8H, C5H4),
4.09 (s, 10H, C5H5); 13C NMR (100 MHz, CDCl3, ppm): ꢁ4.35
(Si(CH3)2), 13.05 (CH3), 21.36, 21.64 (CH2SiMe2), 22.85 (CH2eCH3),
25.38, 27.85, 28.10 (eCH2e), 31.21, 33.27, 34.35, 34.71 (CpCH2),
66.35, 66.47, 66.73, 67.21, 67.35, 67.62, 67.86, 68.49 (Cp), 86.25,
87.16, 87.73, 88.28(CpCH2); Anal. Calc. for: C54H78Fe3Si2 (950.93): C,
68.21; H, 8.27; Fe, 17.62. Found: C, 67.82; H, 8.22; Fe, 17.53%.
4.8. General procedure for the synthesis of trinuclear ferrocenyl
based organosilane
A 25 ml round-bottom flask with magnetic stirrer was charged
with 1,10-bis(3-butenyl) alkylferrocene (1 mmol), [4-(alkylferro-
cenyl)butyl]dimethylsilane (2 mmol) and 15 ml dry toluene as
solvent. 30
m
l of the Karstedt catalyst ([Pt]/[SieH] ¼ 3.1 ꢃ10ꢁ6) was
added. The FT-IR spectroscopy was utilized to follow the progress of
the reaction, by monitoring the loss of the SieH absorption. The
reaction mixture was stirred at room temperature until the com-
plete disappearance of SieH bond in FT-IR spectra. The solvent was
evaporated under reduced pressure and the residue purified by
column chromatography with n-hexane as eluant to give the cor-
responding products. Specific details are given for each compound.
4.8.5. 1,10-Bis [4-[[4-(dimethylsilyl)butyl]ethylferrocenyl]butyl]
ferrocene (8e)
4.8.1. 1,10-bis[4-[[4-(dimethylsilyl)butyl]ferrocenyl]butyl]ferrocene
(8a)
From 0.29 g 3a and 0.66 g 6b, 0.61 g of dark orange oil was
obtained in 64% yield. FT-IR (KBr, cmꢁ1): 3088 (CpeH), 2925 (CeH),
1645, 1459 (C]C), 1250, 813 (CeSi), 1025 (Cp), 491 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.04 (s, 12H, Si(CH3)2), 0.48e0.53 (t,
8H, eCH2SiMe2), 1.14e1.16 (t, 6H, CH3), 1.28e1.38 (m, 8H, e
CH2CH2SiMe2), 1.47e1.54 (m, 8H, CpCH2CH2e), 2.27e2.33 (t, 12H,
CpCH2), 3.94e4.03 (m, 24H, Cp); 13C NMR (100 MHz, CDCl3,
ppm): ꢁ4.26 (Si(CH3)2), 13.24 (eCH2CH3), 21.34, 21.57 (CH2SiMe2),
27.57, 27.88 (eCH2e), 31.39, 34.24, 34.46 (CpCH2), 66.35, 66.57,
67.23, 67.56, 67.74, 68.27 (Cp), 86.31, 87.71, 87.43 (CpCH2); Anal.
Calc. for: C54H78Fe3Si2 (950.93): C, 68.20; H, 8.27; Fe, 17.62. Found:
C, 68.56; H, 8.23; Fe, 17.53%.
From 0.29 g 3a and 0.60 g 6a, 0.61 g of dark orange oil was
obtained in 68% yield. FT-IR (KBr, cmꢁ1): 3084 (CpeH), 2918 (CeH),
1694, 1462 (C]C), 1253, 815 (CeSi), 1099 (Cp), 506 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.03 (S, 12H, Si(CH3)2), 0.48e0.54 (t,
8H, eCH2SiMe2), 1.29e1.40 (m, 8H, eCH2CH2SiMe2), 1.48e1.58 (m,
8H, CpCH2CH2e), 2.29e2.33 (t, 8H, CpCH2), 4.03 (d, 8H, J ¼ 1.3 Hz,
C5H4), 4.05 (d, 8H, J ¼ 1.3 Hz, eCH2C5H4), 4.09 (s, 10H, C5H5); 13C
NMR (100 MHz, CDCl3, ppm): ꢁ4.30 (eSi(CH3)2), 21.11, 21.64
(CH2SiMe2), 28.21, 28.33 (eCH2e), 34.09, 34.43 (CpCH2), 66.43,
66.76, 66.83, 67.58, 67.60 (Cp), 87.42, 87.56 (CpCH2); Anal. Calc. for:
C
50H70Fe3Si2 (894.82): C, 67.11; H, 7.88; Fe, 18.72. Found: C, 66.77;
H, 7.83; Fe, 18.84%.
4.8.6. 1,10-Bis[4-[[4-(dimethylsilyl)butyl]ethylferrocenyl]butyl]
ethylferrocene (8f)
4.8.2. 1,10-bis[4-[[4-(dimethylsilyl)butyl]ferrocenyl]butyl]
ethylferrocene (8b)
From 0.32 g 3b and 0.66 g 6b, 0.61 g of dark orange oil was
obtained in 62% yield. FT-IR (KBr, cmꢁ1): 3099 (CpeH), 2958 (CeH),
1696, 1466 (C]C), 1256, 813 (CeSi), 1080 (Cp), 492 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.03 (s, 12H, Si(CH3)2), 0.49e0.53 (t,
8H, eCH2SiMe2), 1.13e1.18 (t, 9H, CH3), 1.30e1.36 (m, 8H, e
CH2CH2SiMe2), 1.46e1.53 (m, 8H, CpCH2CH2), 2.25e2.37 (m, 14H,
CpCH2), 3.95e4.04 (m, 23H, Cp); 13C NMR (100 MHz, CDCl3,
ppm): ꢁ4.31 (Si(CH3)2), 13.13, 13.53 (eCH2CH3), 21.10, 21.65 (CH2e
SiMe2), 28.10, 28.24 (eCH2e), 30.58, 34.01, 34.25 (CpeCH2), 65.21,
65.75, 66.17, 66.55, 66.83, 66.96, 67.51, 67.83, 67.92 (Cp), 86.37,
86.44, 87.26, 87.49, 88.14 (CpeCH2); Anal. Calc. for: C56H82Fe3Si2
(978.98): C, 68.71; H, 8.44; Fe, 17.11. Found: C, 68.38; H, 8.39; Fe,
17.01%.
From 0.32 g 3b and 0.60 g 6a, 0.58 g of dark orange oil was
obtained in 63% yield. FT-IR (KBr, cmꢁ1): 3089 (CpeH), 2924 (CeH),
1650, 1457 (C]C), 1250, 817 (CeSi), 1026 (Cp), 506 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.03 (S, 12H, Si(CH3)2), 0.49e0.53 (t,
8H, CH2SiMe2), 1.12e1.16 (t, 3H, CH3), 1.30e1.35 (m, 8H,
CH2CH2SiMe2), 1.48e1.54 (m, 8H, CpCH2CH2), 2.29e2.35 (m, 10H,
CpCH2), 3.87e4.00 (m, 7H, C5H4, C5H3), 4.04e4.05 (d, 8H, C5H4),
4.10 (s, 10H, C5H5); 13C NMR (100 MHz, CDCl3, ppm): ꢁ4.29
(-Si(CH3)2), 13.74 (CH3), 21.17, 21.64 (CH2SiMe2), 27.98, 28.35 (e
CH2e), 30.38, 33.99, 34.21, 34.35 (CpCH2), 65.32, 65.83, 66.58,
66.76, 67.14, 67.32, 67.38, 67.60 (Cp), 86.14, 87.38, 87.56, 88.28
(CpCH2); Anal. Calc. for: C52H74Fe3Si2 (922.87): C, 67.68; H, 8.08; Fe,
18.15. Found: C, 67.36; H, 8.12; Fe, 18.07%.
4.8.7. 1,10-Bis[4-[[4-(dimethylsilyl)butyl]ethylferrocenyl]butyl]
propylferrocene (8g)
4.8.3. 1,10-bis[4-[[4-(dimethylsilyl)butyl]ferrocenyl]butyl]
propylferrocene (8c)
From 0.34 g 3c and 0.66 g 6b, 0.56 g of dark orange oil was
obtained in 56% yield. FT-IR (KBr, cmꢁ1): 3084 (CpeH), 2923 (CeH),
1639, 1452 (C]C), 1251, 819 (CeSi), 1101 (Cp), 493 (CpeFe); 1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.03 (S, 12H, Si(CH3)2), 0.51e0.53 (t,
8H, CH2SiMe2), 0.91e0.93 (t, 3H, CpCH2CH2CH3), 1.15e1.18 (t, 6H, e
CpCH2CH3), 1.31e1.35 (m, 8H, CH2CH2SiMe2), 1.47e1.53 (m, 10H,
CpCH2CH2), 2.25e2.36 (m, 14H, CpCH2), 3.94e4.04 (m, 23H, Cp);
13C NMR (100 MHz, CDCl3, ppm): ꢁ4.31 (Si(CH3)2), 13.24, 13.67 (e
CH2CH3), 21.13, 21.28 (CH2SiMe2), 22.05, 26.78, 28.03 (eCH2e),
31.38, 31.52, 34.28, 34.36 (CpCH2), 65.59, 66.46, 66.58, 67.15, 67.34,
From 0.34 g 3c and 0.60 g 6a, 0.55 g of dark orange oil was
obtained in 59% yield. FT-IR (KBr, cmꢁ1): 3088 (CpeH), 2923 (CeH),
1681,1455 (C]C),1251, 817 (CeSi),1102 (Cp), 490 (CpeFe); 1H NMR
(400 MHz, CDCl3, ppm): ꢁ0.03 (s, 12H, Si(CH3)2), 0.48e0.51 (t, 8H,
CH2SiMe2), 0.90e0.93 (t, 3H, CH3), 1.31e1.34 (m, 8H,
CH2CH2SiMe2), 1.44e1.55 (m, 10H, CpCH2CH2), 2.30e2.34 (t, 10H,
CpCH2), 3.85e4.00 (m, 7H, C5H4, C5H3), 4.03e4.05 (d, 8H, C5H4),
4.08 (s, 10H, C5H5); 13C NMR (100 MHz, CDCl3, ppm): ꢁ4.28 (e

44
R. Teimuri-Mofrad et al. / Journal of Organometallic Chemistry 758 (2014) 36e44
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67.49, 67.58, 67.78, 68.32 (Cp), 86.31, 86.42, 87.15, 87.41, 88.25
(CpCH2); Anal. Calc. for: C57H84Fe3Si2 (993.00): C, 68.94; H, 8.53; Fe,
16.87. Found: C, 68.57; H, 8.48; Fe, 16.79%.
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From 0.35 g 3d and 0.66 g 6b, 0.65 g of dark orange oil was
obtained in 65% yield. FT-IR (KBr, cmꢁ1): 3084 (CpeH), 2924 (CeH),
1644, 1452 (C]C), 1256, 810 (CeSi), 1096 (Cp), 492 (CpeFe);1H
NMR (400 MHz, CDCl3, ppm): ꢁ0.03 (s, 12H, Si(CH3)2), 0.50e0.53 (t,
8H, CH2SiMe2), 0.90e0.94 (t, 3H, CpCH2CH2CH2CH3), 1.15e1.19 (m,
6H, CpCH2CH3), 1.30e1.36 (m, 10H, CpCH2CH2CH2), 1.48e1.55 (m,
10H, CpCH2CH2), 2.28e2.35 (m, 14H, CpCH2), 3.84e4.04 (m, 23H,
Cp); 13C NMR (100 MHz, CDCl3, ppm): ꢁ4.33 (Si(CH3)2), 13.18, 13.66
(CH2CH3), 21.14, 21.32 (CH2SiMe2), 21.64, 26.39, 27.84, 28.15 (e
CH2e), 31.25, 31.38, 34.36, 34.65 (CpCH2), 65.48, 65.68, 67.26, 67.35,
67.53, 67.65, 67.94, 68.31, 68.44 (Cp), 86.28, 87.11, 87.36, 87.73,
88.21(CpCH2); Anal. Calc. for: C58H86Fe3Si2 (1007.03): C, 69.18; H,
8.61; Fe, 16.64. Found: C, 68.79; H, 8.56, Fe, 16.55%.
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T. Yamauchi, N. Tsubokawa, Colloids Surf. Physicochem. Eng. Asp. 441 (2014)
474e480;
Acknowledgment
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Polymers, Wiley-Interscience, Hoboken, NJ, 2007.
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We gratefully acknowledge the financial support for this work
by the Research Council of University of Tabriz. The authors deeply
thank Miss Sana Farhoudian for her careful review and with special
thanks to Dr. K. Asadpour for his helpfull suggestion in electro-
chemical field of this work.
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