Synthesis, characterization, and solid-state polymerization properties of two diacetylene derivatives containing phenyl ferrocene

Article abstract of DOI:10.1016/j.jorganchem.2014.05.030

Two diacetylene complexes, 1, 4-bis(3-ferrocenylphenyl)-1,3-butadiyne(4a) and 1,4-bis(4-ferrocenylphenyl)-1,3-butadiyne (4b), were prepared in this study. 4-(Iodoethynylene) phenylene) ferrocene (4b₁) was also obtained. The acetylene complex 4b

Full text of DOI:10.1016/j.jorganchem.2014.05.030

Accepted Manuscript
Synthesis, characterization, and solid-state polymerization properties of two
diacetylene derivatives containing phenyl ferrocene
Hui Liu , Huanhuan Li , Tiesheng Li , Yong Li , Yangjie Wu , Shuji Okada , Hachiro
Nakanishi
PII:
S0022-328X(14)00267-8
10.1016/j.jorganchem.2014.05.030
JOM 18602
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 15 April 2014
Revised Date: 23 May 2014
Accepted Date: 24 May 2014
Please cite this article as: H. Liu, H. Li, T. Li, Y. Li, Y. Wu, S. Okada, H. Nakanishi, Synthesis,
characterization, and solid-state polymerization properties of two diacetylene derivatives containing
phenyl ferrocene, Journal of Organometallic Chemistry (2014), doi: 10.1016/j.jorganchem.2014.05.030.
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ACCEPTED MANUSCRIPT
Graphic Abstract
(PPh3)2PdCl2 , CuI
KOH, toluene
75-80oC
TMED, THF
CuI
ArC C
OH
ArC CH
Ar
Ar
ArBr
2
OH
4
1
2
3
a
Ar =
Ar =
Fe
Fe
b
Two diacetylene complexes , 1,4-bis(3- ferrocenylphenyl)- 1,3-butadiyne(4a) and 1,4-
bis(4-ferrocenylphenyl)-1,3- butadiyne (4b), have been prepared. The solid-state
polymerization properties of 4a and 4b were also investigated.

ACCEPTED MANUSCRIPT
Synthesis, characterization, and solid-state polymerization properties
of two diacetylene derivatives containing phenyl ferrocene
Hui Liu, a,b Huanhuan Li, a Tiesheng Li, *a Yong Li, a Yangjie Wu, a Shuji Okada cand
Hachiro Nakanishi c
*
a College of Chemistry and Molecular Engineering, Zhengzhou University,
Zhengzhou, 450001,P.R. China. E-mail: lts34@zzu.edu.cn.
b Department of Chemistry, Zhengzhou Normal University, Zhengzhou, 450044,P.R.
China. E-mail: lh610@ zzu.edu.cn.
c Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,2-
1-1 Katahira, Sendai 980-8577, Japan. E-mail: okadas@yz.yamagata-u.ac.jp,
hnakanis@tagen.tohoku.ac.jp.
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Synthesis, characterization, and solid-state polymerization properties
of two diacetylene derivatives containing phenyl ferrocene
Hui Liu, a,b Huanhuan Li, a Tiesheng Li, *a Yong Li, a Yangjie Wu, a Shuji Okada cand
Hachiro Nakanishi c
*a College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou,
450001, P.R. China. E-mail: lts34@zzu.edu.cn.
b Department of Chemistry, Zhengzhou Normal University, Zhengzhou, 450044, P.R.
China. E-mail: lh610@ zzu.edu.cn.
c Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,2-
1-1 Katahira, Sendai 980-8577, Japan. E-mail: okadas@yz.yamagata-u.ac.jp,
hnakanis@tagen.tohoku.ac.jp
Abstract
Two diacetylene complexes, 1, 4-bis(3-ferrocenylphenyl)-1,3-butadiyne(4a) and 1,4-
bis(4-ferrocenylphenyl)-1,3-butadiyne (4b), were prepared in this study. 4-(Iodo
ethynylene) phenylene) ferrocene (4b1) was also obtained. The acetylene complex 4b1
was an important intermediate for the synthesis of 4b. The molecular structures of 4a
and 4b1 were determined by single-crystal X-ray studies, and the solid-state
polymerization properties of the complexes were investigated.
Keywords: Diacetylene complexesꢀ Ferroceneꢀ Cyclic voltammetryꢀ Solid-state
polymerization
* ꢁElectronic supplementary information (ESI) available: View along the c axis showing the
organization of 4b1 in the crystalline state(Fig. S1) , Powder XRD patterns of 4b and its partial
polymer(Fig. S2) , UV spectra of 4b cast film irradiated by 254 nm (Fig. S3) and heated at 80ꢂat
different time(Fig. S4). CCDC reference numbers 836849 - 836850.
2

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1. Introduction
Polydiacetylenes (PDAs) are uniquely conjugated with highly crystalline features
and display important electronic and nonlinear optical properties [1]. PDAs may be
applied in molecular electronics, optoelectronic devices, and chemical sensors [2].
Given the rapid progress research in this active field, the design and synthesis of new
molecular materials is the subject of current interest. PDAs can be obtained by
topological polymerization of butadiyne compounds [3]. In principle, when the
molecular alignment satisfies the appropriate alignment (Scheme 1), single crystals of
butadiyne compounds can undergo 1,2-addition or 1,4-addition reaction in the solid
state to produce PDAs by thermal and photochemical irradiation. However, tailoring
molecular spacings and orientations in the resultant crystals is difficult to achieve [4].
Despite the high electron transmission efficiency of PDAs, their thermal and
photochemical instability also has severe drawbacks [5]. Results obtained show that all
side-chain groups have a significant influence on the thermal stability and solid-state
polymerization of the products (PDAs) [6]. Many functional groups have been
introduced into butadiyne compounds to design novel architecture [7]. In previous
studies, we used substituted carbazolyl [8]and pyridyl groups [9] to prepare PDAs. The
design of such DAs is based on the premise that the aromatic side group benefits the
backbone conjugation and provides effective conjugation lengths.
Molecular wires comprising mixed-valence metallic fragments have been
developed as a new promising class of nonlinear optical materials [10]; these wires have
attracted significant research attention because they combine the advantages of both
organic molecules and inorganic semiconductors [11]. The ferrocenyl group (Fc) has
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strong electron donating properties [12]and exhibits reversible one-electron transfer
electrochemical behavior [13]. Ferrocene derivatives constitute a family of new
functional materials because of their high thermal stability, good solubility and
excellent electrochemical property [14]. Since the first report on diferrocenylacetylene
[15], the interest in metal-capped linear polycarbon chains as models for materially
useful material compounds has dramatically increased [9,16]. Some obsvervations
reported the synthesis and polymerization of conjugated ferrocenylacetylenes
compounds and the resulting polymers exhibit a remarkable stability against air and
thermal treatment [17]. Our research group has recently initiated a program for phenyl
ferrocene complexes. The phenyl ferrocene moiety, by virtue of its aromatic interactions
with adjacent molecules can increase the probability that the monomer may be stacked
appropriately in the crystal for topochemical polymerization. As a continuation of our
attempts to the design of ferrocene-based oligoacetylenic complexes materials, the
present paper describes the synthesis, characterization, and solid-state polymerization
properties of two diferrocenylacetylene complexes.
2. Experimental
2.1. Materials and methods
All chemicals used were of reagent grade and were obtained from commercial
sources. Solvents were distilled from appropriate drying agents under nitrogen, and all
reactions were run under dry nitrogen. The starting compounds (3-bromophenyl)
ferrocene (1a) [18] ꢃ(4-bromophenyl) ferrocene (1b) [18]ꢃ2-methyl-4-(3 (ferrocenyl)
phenyl)-3-butdiyn-2-ol (2a) [9] , 2-methyl-4-(4-(ferrocenyl) phenyl)-3-butdiyn-2-ol (2b)
[9] , (3-ethyny phenylene) ferrocene (3a) [9] and (4-ethyny phenylene) ferrocene (3b) [9]
were prepared by reported procedures.
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Melting points were measured using a WC-1 microscopic apparatus and are
reported were uncorrected. C, H, and N analyses were performed on a FLASH EA1112
analyzer. Infrared spectra were recorded on a Bruker VECTOR22 spectro-photometer in
1
KBr pellets. H NMR and 13C NMR spectra were recorded on a Bruker DPX-400
spectrometer in CDCl3 with TMS as an internal standard. Mass spectral data were
acquired on an LC-MSD-Trap-XCT instrument. The X-ray measurements were made
on a Rigaku RAXIS-IV imaging plate area detector with graphite monochromated Mo-
Ka radiation (λ= 0.71073 Ǻ). Photo-chemical polymerizations were conducted under
UV light (peak intensity: 254 nm) and on a cold plate that maintained the sample
temperature at approximately 5 °C. The X-ray diffractometry (XRD) experiments were
performed on a Rigaku Saturn 724 area-detector diffractometer using graphite-
monochromated Mo-Ka radiation.
2.2. Preparation of DA thin films
Quartz slides were cleaned prior to modification by sonication in deionized water,
ethanol, and acetone. The slides were subsequently dried in a stream of nitrogen.
Diacetylene monomer 4a or 4b was added to a flask containing CHCl3. The solution
was stirred for 20 min, and the resulting solution was filtered through a 0.2 ꢀm Teflon
filter and spin-coated onto fresh quartz slides. The films were dried in a vacuum at room
temperature.
2.3. UV measurements
The UV spectra of the monomers were measured before and after UV irradiation or
annealing. Cast films containing the sample on quartz slides were prepared and then
irradiated with a UV source (254 nm) for different amounts of time.
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2.4. Electrochemical measurements
Electrochemical experiments were performed with a CHI 650A electrochemical
analyzer (CH Instruments, USA). A conventional three-electrode electrochemical cell
was used with a glassy carbon electrode (GCE) as the working electrode, a saturated
calomel electrode (SCE) as the reference electrode, and a platinum wire as the auxiliary
electrode. The number of electrons transferred for the compounds were estimated by
comparing the peak height of the respective ferrocene redox wave with an equal
concentration of the ferrocene standard added in the same system. All experiments were
carried out at a temperature of 25 °C.
2.5. Preparation of complexes (4a, 4b)
2.5.1. Preparation of 1,4-bis(3 ferrocenylphenyl)-1,3-butadiyne (4a)
A 1.14 g portion of 3a (4 mmol) was placed in a three-necked flask and dissolved in 20
mL of dry THF with oxygen. N,N,N,N-Tetramethyl ethylenediamine (1 mL) was added
to the mixture, followed by CuI (1 mmol). The reaction solution was stirred thoroughly
at room temperature, and oxygen was bubbled through the solution. The reaction was
monitored by TLC (petroleum ether / ethyl acetate, 15:1) and found to be complete after
30 min. The compound was passed through a silica gel column using petroleum ether /
ethyl acetate (15:1) as the eluent and 4a was obtained in pure form as a brown yellow
solid. The yield of the product was 30%. m. p. 186-188 °C. 1HNMR (CDCl3, 400 MHz)
δH 7.64 (1H, s, C6H4), 7.47 (1H, d, JH-H = 6.8 Hz, C6H4), 7.35 (1H, d, JH-H = 6.0 Hz,
C6H4), 7.24 (1H, m, C6H4), 4.66(2H, t, JH-H = 1.8 Hz, C5H4), 4.35(2H, t, JH-H = 1.6 Hz,
C5H4), 4.07 (5H, s, C5H5). 13CNMR (CDCl3, 100 MHz) δC 139.9 (Ph), 129.8 (Ph),
129.0(Ph), 128.5 (Ph), 126.9 (Ph), 121.7 (Ph), 84.0 (Ph-Cꢄ), 81.8 (C5H4), 73.6 (CꢄC),
69.7 (C5H4), 69.3 (C5H4), 66.5 (C5H4). MS: 571[M+H]+. Analytical calculation for
C36H26Fe2 C, 75.58%; H, 4.50%; Found: C, 75.80%; H, 4.75%.
2.5.2. Preparation of 1,3-bis(3-ferrocenylphenyl)-1,3-butadiyne (4b)
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4b was synthesized using the same method used for 4a synthesis. The starting
material in this case was 3b (1.14 g, 4 mmol). The product obtained was called 4-(iodo
1
ethynylene) phenylene ferrocene (4b1). The yield of the product was 35%. HNMR
(CDCl3, 400 MHz) δH 7.36 (2H, d, JH-H = 2.0 Hz,C6H4), 7.23 (2H, d, JH-H = 8.0
Hz,C6H4), 4.61 (2H, t, JH-H =1.8 Hz, C5H4), 4.31 (2H, t, JH-H = 1.6 Hz,C5H4), 4.00 (5H,
s, C5H5); 13CNMR (CDCl3, 100 MHz) δC 140.5 (Ph), 132.2 (Ph), 125.6 (Ph), 120.4
(Ph), 94.3 (Ph-Cꢄ), 83.9 (C≡C), 69.7 (C5H4), 69.6 (C5H4), 69.3 (C5H4), 66.5 (C5H4).
MS: 414 [M+]. Analytical calculation for C18H13FeI C, 52.47%; H, 3.18%; Found: C,
52.75%; H, 3.48%.
Repeating the above experiment, another coupling compound designated 4b was
isolated as a brown powder using hexane/chloroform (3/1) as the eluent. The yield of
the product was 30%.1H NMR (CDCl3, 400 MHz) δH 7.45 (2H, d, JH-H = 2.0 C6H4),
7.43 (2H, d, JH-H = 8.0 C6H4), 4.67 (2H, d, JH-H = 2.0 C5H4), 4.37 (2H, d, JH-H = 1.8
C5H4), 4.05 (5H, s, C5H5); 13CNMR (CDCl3, 100 MHz) δC 141.0 (Ph), 132.5 (Ph),
125.8 (Ph), 118.8 (Ph), 82.1 (Ph-Cꢄ), 76.6 (C≡C), 73.6 (C5H4), 69.8 (C5H4), 69.6
(C5H4), 66.6 (C5H4). MS: 570 [M+]. Analytical calculation for C36H26Fe2 C, 75.58%;
H, 4.50%; Found: C, 75.85%; H, 4.80%.
3. Results and discussion
3.1. Synthesis of 4a, 4b and 4b1
4a and 4b were synthesized according to the route shown in Scheme 2.
Sonogashira coupling reaction of 2-methyl-1,3-butadyne-2-ol with 1 produced 2-
methyl-4-(3 or 4-(ferrocenyl)phenyl)-3-butdiyn-2-ol (2) after conversion of 2 to (3 or 4-
ethyny phenylene) ferrocene (3) under a strong base. 4a and 4b were obtained by
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Cadiot-Chodkiewicz coupling reaction [18] of 3a and 3b using CuI/TMED as a catalyst.
Interestingly, we obtained 4b1 during 4b synthesis. Wai-Yeung et al. [16] obtained 4b
through simultaneous oxidative coupling of 4-ethynylphenyl ferrocene in the presence
of a trace amount of atmospheric O2 and studied the crystal structure of this compound.
Hay used CuI as an oxidizing agent [19] in the larger-scale preparative examples. Thus,
we believe that the iodide anion is oxidized into iodine to produce 4b1 [20] , which
undergoes a coupling reaction to produce 4b.
3.2. Crystal Structures of 4a and 4b1
X-ray crystallography images of the molecular structures of 4a and 4b1 are
illustrated in Figs. 1 and 2, respectively. The crystal structure data and important bond
parameters, along with selected dihedral angles, are tabulated in Tables 1–3. The
structure of 4a reveals a 1,3-butadiyne linear chain with two ferrocenylphenyl
substituents in positions 1 and 4 of the chain. Each ferrocenylphenyl moiety is located
on opposite sides of the mean plane and C5H4 rings, with a symmetry center at the mid-
point of the C(18)-C(18A) bond. The C(17)–C(18) bond is 1.190(9) Å, whereas the
C(18) –C(18A) bond [1.3746(35) Å] distance is similar to that observed in 1,4-
diferrocenyl-1,3-butadiyne [21] [1.198(4) and 1.373(3) Å] and 4b [16] [1.184(8) and
1.391(14) Å], respectively.
When viewed along the crystallographic a axis, the structure of 4a resembles
stacks(Fig. S1see the supporting information). The presence of a layer-by-layer stacking
arrangement is evident. The carbon-to-carbon distance (dCC) recommended for 1,4-
propagation during polymerization is 6.0108(44) Å (Fig. 3). This distance is larger than
the upper limit of the geometrical criteria for polymerizability (Scheme 1, d < 5 Ǻ).
Thus, it is too far way from one another for diacetylenic units to undergo topochemical
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polymerization.
Each molecule of 4b1 consists of a ferrocene unit and an iodine acetylene group
[C(17)–C(18) = 1.180(7) Å] appended to the phenylene group ring in the 1,4-position.
However, the structure of 4b1 is different from that of 4a in that DAs now pile up in
stacks (Fig. S2 see the supporting information).
In these cases, the cyclopentadienyl rings of the ferrocenyl group are essentially
planar and the tilt angles lie within the narrow range of 0.1°–1.8°. No intermolecular
interactions were observed in the crystal lattices of the complexes.
3.3. Electrochemical tests
The electrochemical behavior of 4a, 4b and ferrocene at the GCE electrode were
investigated using cyclic voltammetry (CV). Initial CV scans from 0.0 to 1.1 V showed
only one well-defined and stable redox wave, which corresponds to the Fc+/Fc redox
process. The electrochemical parameters of the complexes are summarized in Table 4.
The formal potentials [E0 = (Epa + Epc)/2] of 4a and 4b (0.514 V, 0.513 V) are very
close, which indicates that the ferrocene subunits in both cases are in equivalent
environments. The two compounds undergo a single-step two-electron redox reaction.
The formal potentials of 4a (4b) also shift to more positive potentials compared with
that of ferrocene, which suggests that unsaturation of the ethynyl bridge prevents the
removal of electrons in the complexes [22].
3.4. Solid-state polymerization
3.4.1. XRD studies
The XRD patterns of 4a and the corresponding polymer after UV irradiation (254
nm) and heating (120 °C) is shown in Fig. 4. The sharp XRD peaks of 4a at a low
diffraction angle (2θ = 5°) indicate its crystalline nature. After UV irradiation or heating
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for 30 min, the monomer crystalline peaks completely disappeared. These data support
the large movement of the monomer units from their lattice points to decrease the
crystallinity in the course of the solid-state polymerization. Similar spectral and XRD
changes during UV irradiation or annealing to those of 4a were also observed for 4b
(Fig. S3 see the supporting information), suggesting that these monomers polymerize in
a similar by manner in the solid state.
3.4.2. UV spectroscopy
UV spectra of the monomers were measured before and after UV irradiation. As
shown in Fig. 5, three UV absorption peaks of 4a appear at 292, 314, and 334 nm; these
peaks arise from π-π٭ electronic transitions of the relevant organic groups [16]. The
absorbance of the peaks decreased and shifted toward longer wavelengths with
increasing irradiation time. However, although the absorption tail became broader and
extended nearer the infrared region, no obvious absorption peak was observed at long
wavelengths. These results suggest that solid-phase polymerization does not proceed via
1,4-addition; instead, polymerization may occur through some irregular pathway to
react with C≡C bonds. UV light may be unable to penetrate through the crystals because
of the polymers produced on the complex surfaces.
Sample (4a) was pelletized and heated at different temperatures (from 80 °C to
120 °C) in an oven before annealing. The color of the samples changed from deep red to
nearly black during polymerization when heated above 80 °C (Fig. 6). This finding is
inconsistent with the expected color of 1,4-addition polymerization reaction products
[23]. The products were taken out of the oven at certain time intervals and their UV
spectra were recorded. Bands at 292, 314, and 334 nm, indicating conjugated
phenylferrocenyl groups, became weak and the absorption tail extended toward the
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long-wavelength region, where no absorption peak of polydiacetylene was observed,
and broadened. This result proves that polymerization takes place with the extension of
π-conjugation, which indicates that solid-state polymerization occurs through a
mechanism inconsistent with that of 1,4-addition. Spectral changes similar to those of
4a were observed during UV irradiation and annealing of 4b, which indicates that 4b
polymerizes in the same manner (Fig. S 4-5 see the supporting information)
3.4.3. Micrographical study
Fig. 7 shows optical micrographs of 4a obtained before and after heating for 30
min. The polymer shows a regular round loop. We propose that the polymer aggregates
and assembles to form a certain regular shape.
4. Conclusions
We have successfully synthesized two diacetylenes functionalized with phenyl
ferrocene moieties. 4b1, an important intermediate for 4b synthesis, was also obtained.
The phenyl ferrocene side groups of 4a and 4b were linked directly to the diacetylene
backbone to obtain maximum π-conjugated effects. The two compounds underwent a
single-step two-electron redox reaction. The crystal structure of 4a reveals inhibition of
topochemical polymerization. The meta and para positions of the diacetylenes indicate
a polymerization pattern inconsistent with that of 1,4-addition, which demonstrates the
importance of steric factors in solid-state polymerization reactions.
Acknowledgements
This work was partially supported by the Fund for Outstanding Younger Scholar of
Henan Province(074100510015).
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Electronic Conference on Trends in Organic Chemistry (ECTOC-1), ed. H. S.
Rzepa and J. M. Goodman (CDROM), 1995, Royal Society of Chemistry
publications. See also http://www.ch.ic.ac.uk/ectoc/papers.
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Figure Captions
Scheme1 Solid-state polymerization of diacetylene (d <5Ǻ, D<4Ǻ and φꢇ45˚).
Scheme 2 Syntheses of compounds 4a and 4b.
Fig.1. An ORTEP diagram of 4a with a probability of 50%.
Fig. 2. An ORTEP diagram of 4b1 with a probability of 50%.
Fig. 3. The carbon-carbon distance (dCC) of 4a in the crystalline state for 1,4-
propagation during polymerization.
Fig. 4. Powder XRD patterns of 4a(a). its partial polymer obtained by UV irradiation
254 nm (b) and by heating at 120°C for 30min (c).
Fig.5. UV spectra of 4a cast film by irradiated at 254 nm with different time.
Fig.6.UV spectra of 4a cast film heated at 80ꢂat different time.
Fig.7.Optical micrograph of 4a cast film beforeand after heating for 30min.
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R
R
R
D
h ν o r
ꢁ
R
d
R
R
R
d
R
φ
polymer
monomer
Scheme1 Solid-state polymerization of diacetylene (d <5Ǻ, D<4Ǻ and φꢇ45˚).
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(PPh3)2PdCl2 , CuI
ArC C
KOH, toluene
75-80oC
TMED, THF
CuI
OH
ArC CH
Ar
Ar
ArBr
2
OH
4
1
2
3
a
Ar =
Ar =
Fe
Fe
b
Scheme 2 Syntheses of compounds 4a and 4b.
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Fig.1. An ORTEP diagram of 4a with a probability of 50%.
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Fig. 2. An ORTEP diagram of 4b1 with a probability of 50%.
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Fig. 3. The carbon-carbon distance (dCC) of 4a in the crystalline state for 1,4-
propagation during polymerization.
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Fig. 4. Powder XRD patterns of 4a(a). its partial polymer obtained by UV irradiation
254 nm (b) and by heating at 120°C for 30min (c).
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Fig.5. UV spectra of 4a cast film by irradiated at 254 nm with different time.
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Fig.6. UV spectra of 4a cast film heated at 80ꢂat different time.
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A
B
Fig.7. Optical micrograph of 4a cast film before(A) and after (B) heating for 15min.
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Table 1 Summary of Crystal structure data for complexes 4a and 4b1
4a
C36H26Fe2
570.27
4b1
C18 H13 FeI
412.03
Formula
Mr
crystal size (mm)
a (Å)
0.40 x 0.20 x 0.20
7.9868(6)
17.0952(13)
20.1909(13)
90
0.18 x 0.16 x 0.16
15.7092(4)
13.4346(4)
14.4912(4)
90
b (Å)
c (Å)
α (o)
β (o)
90
90
2756.8(4)
4
97.224(2)
90
3034.04(15)
8
γ (o)
U(Å3)
Z
space group
Dcalc (g cm-3)
Μ(Mo-Ka) (mm-1)
θ range (o)
Pbca
1.374
1.075
P2(1)/c
1.804
3.015
2.97-26.37
13923
2.99-26.37
7919
Number of data collected
Number of unique data
Observed reflections [I > 2σ(I)]
No. of parameters
R1,wR2 [I > 2σ(I)]
R1,wR2 (all data)
peak/hole (e·Å-3)
2810
2145
172
6188
4423
361
0.0377 0.0793
0.0555 0.0874
0.189/ -0.346
0.0433 0.0825
0.0703 0.0939
0.576 / -0.816
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Table 2 Selected bond lengths (Å) and angles(°) for complexes 4a.
Fe (1)-Cp
Fe (1)-C5H4
C(17)-C(18)
C(18)-C(18)
Dihedral angles (°) between
planes
1.6345
1.6450
1.190(9)
1.3746(35)
A and B
A and C
B and C
1.0
2.8
2.2
Planes: A, C(1)- C(2)- C(3)-C(4)-C(5); B, C(6)- C(7)- C(8)-C(9)-C(10); C, C(11)-
C(12)- C(13)-C(14)-C(15)-C(6).
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Table 3 Selected bond lengths (Å) and angles(°) for complexes 4b1.
Fe (1)-Cp
Fe (1)-C5H4
C(17)-C(18)
Dihedral angles (°) between
planes
1.6359
1.6414
1.180(7)
A and B
A and C
B and C
0.1
7.3
7.3
Planes: A, C(1)- C(2)- C(3)-C(4)-C(5); B, C(6)- C(7)- C(8)-C(9)-C(10); C, C(11)-
C(12)- C(13)-C(14)-C(15)-C(6).
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Table 4 Electrochemical dataa for ferrocene and ferrocene derivatives
b
ipc / ipa
△
Compound
Fc
Epa/V Epc/V
E
p/V
E0 b /V
0.541 0.418
0.123
0.479
1.01
0.577 0.445
0.606 0.419
0.132
0.185
0.514
0.513
1.32
1.20
4a
4b
a All potentials are referred to the saturated calomel electrode (SCE) in CH2Cl2
+ 0.1 mol/L tetra-n-butylammonium hexafluorophosphate (TBHP) solution,
v=100 mV/s.
b
△
Ep = (Epa - Epc), E0 = (Epa + Epc)/2
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