Alkynylation of ferrocene by terminal alkynes. Part I. A simple one-step synthesis of ferrocenylacetylenes

Article abstract of DOI:10.1016/j.jorganchem.2010.09.039

Ferrocene reacts with terminal alkynes in the presence of copper and iron salts to give 1-ferrocenyl-2-R-alkynes (R - substituent). This direct cross-coupling of ferrocenyl and alkynyl moieties allows for the preparation of ferrocenyl substituted alkynes

Full text of DOI:10.1016/j.jorganchem.2010.09.039

Journal of Organometallic Chemistry 696 (2011) 468e472
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Communication
Alkynylation of ferrocene by terminal alkynes. Part I. A simple one-step synthesis
of ferrocenylacetylenes
*
Victor P. Dyadchenko , Marina A. Dyadchenko, Vladimir N. Okulov, Dmitri A. Lemenovskii
Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 1-3, Moscow 119992, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 17 May 2010
Received in revised form
Ferrocene reacts with terminal alkynes in the presence of copper and iron salts to give 1-ferrocenyl-2-R-
alkynes (R e substituent). This direct cross-coupling of ferrocenyl and alkynyl moieties allows for the
preparation of ferrocenyl substituted alkynes in one step directly from ferrocene and a terminal alkyne
avoiding prior preparation of other derivatives of ferrocene. This new synthetic reaction does not require
special conditions, is promoted by the action of common iron and copper salts, and tolerates the pres-
ence of functional groups in the alkyne.
3
September 2010
Accepted 19 September 2010
Available online 8 October 2010
Ó 2010 Elsevier B.V. All rights reserved.
Keywords:
Ferrocene
Terminal alkyne
Coupling
Ferrocenylacetylenes
Iron(III) chloride
Copper(II) acetate
Alkynylation
1
. Introduction
step syntheses of ferrocenyl substituted alkynes which contain
sensitive functional groups in the organic moiety (for example, Br
[9], HO [10,11]).
Therefore, the development of new synthetic approaches to
1-ferrocenyl 2-R-alkynes remains of indubitable interest. Here we
report a new and unusual synthetic approach to alkynyl substituted
ferrocenes based on cross-coupling of ferrocene with terminal
alkynes and which thus can be named a “direct alkynylation of
ferrocene”.
2
n
Metal mediated C(sp )-C(sp ) (n ¼ 1e3) cross-coupling reac-
tions are in the focus of intensive current research [1], but their
most popular versions (MizorokieHeck, SuzukieMiyaura, and
Stille) are compromised by the formation of an inorganic waste [2].
Direct dehydrogenative CeC coupling provides
waste-free alternative but this reaction has been limited to arenes
that can pre-coordinate to the catalyst [2].
a promising,
Organometallic derivatives of alkynes and specifically the
derivatives containing ferrocenyl group represent interesting
objects from different points of view [3]. However, the preparation
of 1-ferrocenyl substituted 2-R-alkynes (R e substituent different
from ferrocenyl) requires multi-step syntheses such as: the Cu/
Pd-catalyzed cross-coupling reactions of iodo derivatives of ferro-
cenes with 1-alkynes [4,5], modification of beforehand prepared
ferrocenylacetylene [6] and syntheses based on the Mo-catalyzed
metathesis of 1-ferrocenylpropyne [7,8] which is again prepared
from ferrocenylacetylene. Particular concerns come up for multi-
2
. Results and discussion
We have found that a reaction of ferrocene with terminal
alkynes (IaeIe) in the presence of air oxygen and substoichiometric
amounts of iron(III) chloride and copper(II) acetate gives alky-
nylferrocenes (IIaeIIe) (Scheme 1) in one step and under very
mild conditions. It is very important that this new synthetic reac-
tion can be done in a simple bench set-up, is promoted by the
action of common iron and copper salts, and allows for ferrocene
coupling with terminal alkynes containing functional groups.
In Scheme 1, the yields of ferrocenylacetylenes II are given based
on the ferrocene introduced into the reaction. Yields of II based on
the consumed ferrocene are 79e98%. In the case of acetylene (If)
*
Corresponding author. Tel.: þ7 495 939 5379; fax: þ7 495 932 8846.
E-mail address: dyadchenko@org.chem.msu.ru (V.P. Dyadchenko).
0
022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.09.039

V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 696 (2011) 468e472
469
Cu(OAc)2
R
O ; FeCl ; Cu(OAc) H O
R
H
+
Fe
2
3
2
2
Fe
FeCl3
AcO - CH Cl
2
Ia - If
2
Ph
Ph
IIa - IIf
R = Ph (IIa; 28%), 4-Br-C H (IIb; 41%), Me Si (IIc; 56%),
Ph
H
CuCl
Ph
6
4
3
Ia
HOCH2 (IId; 47%), Me (HO)C (IIe; 44%), H (IIf; 5%)
2
Scheme 1. Interaction of ferrocene with 1-alkynes.
O2
H
yield of ferrocenylacetylene (IIf) is very low due to fast trans-
Fe
Fe
formation of copper(II) acetate into deep red polymeric Cu
which does not participate in this reaction.
2
C
2
analogous to Glaser reaction
Ph
We found that the reaction of I to give II occurs only in the
presence of air. If this reaction is carried out in purging argon, II
forms in only trace amounts. These results indicate the participa-
partial
decomposition
Ph
tion of O
2
which can play a role of oxidant.
Fe
It is important that both copper(II) acetate and iron(III) chloride
be introduced in the reaction mixture together. Experiments
with Ia carried out in the presence of only copper salt or only iron
salt do not give IIa.
FeCl2
IIa
Fe
FeCl4
O2
+ Cl
The yields of alkynyl derivatives II depend on many factors,
including the nature of solvent, the ratio of reagents, the temper-
ature, and the duration of reaction. So far we have explored only
a small section of this large cross-matrix of parameters. To optimize
the reaction conditions, we chose a model system comprised of
ferrocene and alkyne Ia.
FeCl3
Fe
Concerning the reaction medium, we found that direct alkyny-
Scheme 2. A tentative mechanism for alkynylation of ferrocene.
lation does proceed in AcOH or in CH
yields. The use of 5:1 (by volume) mixture of AcOH and CH
gave enhanced yields of IIa. If a mixture of CH Cl with a stronger
acid, e.g. CF COOH (13:2 by volume), is used, the compound IIa is
not formed. Therefore, a mixture of AcOH and CH Cl (5:1 by
2
Cl
2
, but it affords IIa in low
2
Cl
2
OMe
OMe
OMe
2
2
Ph
3
FeCl3, FeCl2, Cu(OAc)2 H2O
Ph
+
+
2
2
volume) was used as the solvent in experiments with terminal
alkynes (IaeIe).
H
IIIa (1%)a
Ia
Ph
The molar ratio of reactants has been varied in the limits shown
in Table 2 (see the Experimental part). The following molar ratio,
IIIb (3%)a
aYields are given based on Ia introduced in the reaction.
Scheme 3. Interaction of anisole with phenylacetylene.
ferrocene : FeCl
3
: Cu(OAc)
2
$H
2
O: Ia ¼ 1:0.25:0.5:2, was found to
give the best yield of the target compound IIa (28%).
The optimal duration of alkynylation were determined by TLC
monitoring. Concentration of IIa in the reaction mixture increases
slowly, reaches the maximum after about 18e20 h, and then
diminishes due to decomposition of the product.
Common aromatic substrates such as benzene and its electron-
rich and electron-poor derivatives (anisole, biphenyl, nitrobenzene)
do not afford corresponding disubstituted acetylenes under the
conditions of Scheme 1, and are recovered almost quantitatively
It is noteworthy that in the alkynylation of ferrocene by Ia the
1,4-diphenylbutadiyne (19% based on the Ia introduced into reac-
1
tion) and a small amount of copper phenylacetylenide are formed
as side-products.
As follows from Scheme 1, conditions of the reaction (presence of
oxygen and salts of transition metals) facilitate free radical mecha-
nism including formation of 2-phenylethynyl radicals and their
subsequent interaction with ferrocene or ferrocenium (forming
from reaction mixtures. For example, the reaction of anisole with Ia
gives, after the removal of recovered anisole (91% of the amount
introduced into the reaction) and Ia, a small amount of a complex
mixture of products (5% based on the total mass of anisole and Ia
introduced into the reaction). Gas chromatography analysis of this
þ
mixture with mass detection did not find compounds with the M of
under action of FeCl
radical substitution in ferrocene series proceeds via ferrocenium
12]. In our experiments when we used just ferrocenium tetra-
fluoroborate instead of ferrocene in the reaction with Ia in condi-
tions shown in Scheme 1 we did notobserveformation of compound
IIa. This permits us to propose that alkynylation proceeds via
interaction of 2-phenylethynyl radicals with ferrocene.
3
on ferrocene). Conventional is proposal that
208, i. e. the metoxytolanes. From this mixture, we separated and
characterized two major components: o- (IIIa) and p- (IIIb) isomers
of (1-phenylvinyl)anisole (Scheme 2), which suggests a Friedel-
Crafts type of reaction, similar to the reaction of arylacetylenes with
benzene derivatives mediated by lantanide triflates [13] (Scheme 3).
Direct alkynylation of electron-deficient polyfluoroarenes is
known but occur under different conditions e in the presence of
[
The alkynylation of ferrocene which we found is unusual reac-
tion and does not have analogy.
Mechanism of this reaction is unclear and needs special inves-
tigation. We understand that alkynylation of ferrocene is multi-step
process and now we can only propose one of tentative mechanisms
1
In the ethynylation of ferrocene under the conditions of Scheme 1, FeCl
3
introduced into the reaction mixture is reduced quickly by ferrocene to give FeCl
Therefore, the reactions with benzene and its derivatives were attempted both in
the presence of FeCl and in the presence of FeCl
2
.
(
see Scheme 2).
2
3
.

470
V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 696 (2011) 468e472
a strong base [14]. With regard to ferrocene, it is important that
our alkynylation reaction has general character for different
terminal alkynes, and can be used for the synthesis of functional-
ized ferrocenyl derivatives II (see Scheme 1) in preparative scale.
In conclusion, the direct alkynylation of ferrocene by terminal
alkynes is a new and convenient one-step method competitive to
other published multi-step methods for the preparation of 1-fer-
rocenyl substituted acetylenes because of its simplicity and
cheapness. The advantages of our synthetic method are especially
obvious in comparison with published procedures for the prepa-
ration of IIaeIIe. Functional groups in products IIbeIIe allow for
subsequent modification of ferrocenyl alkynes, which provides
potential access to many other derivatives of ferrocene bearing
the acetylene moiety.
The resulting mixture was poured into a solution of ascorbic
acid (0.5 g) and EDTA disodium salt dihydrate (1.0 g) in 100 ml of
water and extracted with dichloromethane. The extract was
2 4
washed with water, dried over Na SO , and filtered. After the
removal of solvent in vacuo, the residue was subjected to column
chromatography on silica gel (eluentepetroleum etherebenzene
9:1 mixture). The first band afforded a mixture of ferrocene and
1
1,4-diphenylbutadiyne (0.371 g). On the basis of H NMR spectrum,
this mixture contains 0.253 g (45%) of recovered ferrocene and
0.118 g (19% based on Ia introduced in the reaction) of 1,4-diphe-
nylbutadiyne. The second band gave 1-ferrocenyl-2-phenyl-
ꢀ
acetylene (IIa) (0.237 g; 28%), m. p. 125e126 (recrystallized from
ꢀ
ethanol); cf. Ref. [15]: m. p. 127e128 .
1
H NMR: 4.28 (m), 4.29 (s, 2H, C
), 7.36e7.58 (, 5H, Ph); C NMR: 65.35 (Cipso, C ), 68.80 (CH,
5
H
4
þ 5H, Cp), 4.56 (m, 2H,
13
C
C
5
H
H
4
5 4
H
5
4
), 69.97 (CH, C
5
H
5
), 71.41 (CH, C
5
H
4
), 85.74, 88.30 (C^C),
3
. Experimental
þ
1
23.98 (Cipso, Ph), 127.59, 128.39, 132.46 (CH, Ph) cf. Ref. [6]; LDI: M
ꢁ1
286. IR: 2240 cm , weak (C^C).
The following starting materials were used as received: anhy-
drous iron trichloride, 98%, trimethylsilylacetylene, 1,1-dimethyl-
-propyneol (Acros Company), anhydrous iron dichloride, 98%
3
.1.2. Reaction of ferrocene with phenylacetylene (Ia) in argon
2
purge
Reaction was carried out as specified in Section 3.1.1. Argon
purge was used. Ferrocene (0.558 g; 3 mmol) and Ia (0.66 ml;
(
(
Aldrich Company), copper(II) acetate monohydrate, purissimum
VEB Chemie APOLDA). Anhydrous copper(II) acetate was prepared
from monohydrate by removal of water as azeotrop with toluene.
Propargyl alcohol (Acros Company) was redistilled twice under
argon purge before use. Phenylacetylene 98% (Acros Company)
6
mmol in two portions) gave compound IIa (0.013 g; 1.5%).
3
.1.3. Interaction of ferrocene with Ia in acetic acid
Reaction was carried out as specified in Section 3.1.1. Glacial
ꢀ
was distilled under reduced pressure (b. p. 64 /53 mm Hg). Ferro-
ꢀ
cene was recrystallized from petroleum ether (70/100 C) and dried
acetic acid (16 ml) was used as a solvent instead of a mixture of
AcOH and CH
refluxed) for 1.5 h. Compound IIa (0.167 g; 19%) was obtained, m. p.
in vacuum desiccator.
ꢀ
2
Cl
2
. The reaction mixture was stirred at 75 (not
NMR spectra were recorded in CDCl
temperature on Bruker Avance 400 instrument ( H 400 MHz;
00 MHz). Chemical shifts ( , ppm) are given relative to residual
3
solutions at room
1
13
C
ꢀ
125e126 (recrystallized from ethanol).
1
d
13
1
13
proton signals ( H NMR) or C signal ( C NMR) of the solvent. IR
spectra were recorded on UR-20 instrument as suspensions in
Nujol. The LDI spectra were measured on Bruker Daltonics Autoflex
II instrument (laser 337 nm excitation). Gas chromatography of
IIIa and IIIb was carried out on the Finnigan Mat TSQ 7000
instrument.
3
.1.4. Interaction of ferrocene with Ia in CH
Reaction was carried out as specified in Section 3.1.1. Dry
dichloromethane (16 ml) was used as a solvent instead a mixture
of AcOH and CH Cl Anhydrous copper(II) acetate in two
portions: 0.085 g (0.47 mmol) and 0.187 g (1.03 mmol) was used
2 2
Cl
2
2
.
instead of Cu(OAc)
obtained.
2 2
$H O. Compound IIa (0.086 g; 10%) was
Yields of IIaeIIe are given based on ferrocene introduced into
reactions.
Monitoring of reactions was performed by TLC on “Silufol 254”
plates. R values are specified in Table 1.
f
3
.1.5. Variation of molar amounts of reagents in alkynylation of
ferrocene by IIa
All reactions were carried out as specified in Section 3.1.1.
Ferrocene (0.558 g; 3 mmol), dichloromethane (2.6 ml) and glacial
acetic acid (13 ml) were used in each experiment. Results are
summarized in Table 2.
3
3
.1. Alkynylation of ferrocene by phenylacetylene (Ia)
.1.1. 1-Ferrocenyl-2-phenylacetylene (IIa). Typical procedure
Reagents and solvents were mixed in the following order:
ferrocene (0.558 g; 3 mmol), dry dichloromethane (2.6 ml), glacial
acetic acid (13 ml), anhydrous iron trichloride (0.122 g; 0.75 mmol),
copper(II) acetate monohydrate (0.10 g; 0.5 mmol) and phenyl-
acetylene (0.33 ml; 0.31 g; 3 mmol). The reaction mixture was
3.2. Preparation of compounds IIbeIIf
All compounds IIbeIIe were prepared according to the typical
procedure (Section 3.1.1) described for the preparation of IIa. In
stirred for 1 h at ambient temperature, then for 1.5 h under reflux
ꢀ
Table 2
(
temperature of the reaction mixture: 75 ) and cooled to ambient
Yields of IIa in experiments Section 3.1.2. Molar amounts of reagents are specified
per 1 mol of ferrocene.
temperature. Additional portions of copper(II) acetate mono-
hydrate (0.20 g; 1.0 mmol) and phenylacetylene (0.33 ml; 0.31 g;
FeCl
3
Cu(OAc)
2
$H
2
O
PhChCH (Ia)
Yield of IIa, %
3
mmol) were added to the reaction mixture and stirring was
continued for 19.5 h.
First
portion
Additional
portion
First
Additional
portion
portion
2
1.0
1.0
.0
0.7
0.7
e
0.5
0.5
1.0
1.0
1.0
1.0
1.0
1.0
e
0
2
7
15
10
25
28
5
Table 1
e
e
R
f
values for ferrocene and compounds IIaeIIe on “Silufol 254” plates.
0.17
0.17
0.17
0.5
0.17
0.17
0.33
0.33
0.33
0.5
0.33
0.33
1.0
1.0
e
0
0
.5
.25
Compound
Eluent
Ferrocene
IIa
IIb
IIc
Ferrocene
IId
IIe
a
a
a
a
b
b
b
0.25
0.25
1.0
1.0
1.0
R
f
0.34
0.16
0.21
0.20
0.78
0.08
0.10
0.1
a e benzeneepetroleum ether 1:9 by volume; b e benzene.

V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 696 (2011) 468e472
471
each experiment, 0.558 g (3 mmol) of ferrocene, dry dichloro-
methane (2.6 ml), glacial acetic acid (13 ml), anhydrous FeCl
The resulting mixture was poured into a solution of ascorbic
acid (0.5 g) in 100 ml of water and extracted with dichloromethane.
The extract was filtered through Büchner funnel, washed with
3
(
0.75 mmol), Cu(OAc)
2
2
$H O (1.5 mmol in two portions) and
6
mmol of terminal alkyne IbeIe (in two portions) were used.
2 4
water, dried over Na SO , and filtered. After the removal of solvent
Compounds II were purified by column chromatography on silica
gel: IIb and IIc were eluted with petroleum etherebenzene 9:1
mixture; IId and IIe were eluted with benzene.
in vacuo, the residue was subjected to column chromatography on
silica gel (eluentepetroleum etherebenzene 9:1 mixture). The first
colored band (ferrocene and 1,4-diphenylbutaiyne) was discarded.
The second colored band was collected; removal of the solvent
ꢀ
3.2.1. 1-(4-Bromophenyl)-2-ferrocenylacetylene (IIb)
in vacuo gave ferrocenylacetylen (0.031 g; 5%), m. p. 54e55 ,
ꢀ
Reaction was carried out as specified in Section 3.1.1. Ferrocene
cf. Ref. [16]: m. p. 55e56 .
1
and 4-bromophenylacetylene afforded IIb (0.449 g; 41%), m. p.
H NMR: 2.73 (s) (1H), 4.17 (m), 4.21 (s, 2H, C
5 4
H and 5H, Cp),
ꢀ
1
60e161.5 (recrystallized from 95% ethanol). Calculated for
4.41 (m, 2H, C
5
H
4
), cf. Ref. [17].
18
C H13BrFe: C 59.22, H 3.56%. Found: C 59.24, H 3.67%.
1
H NMR: 4.25 (2H, C
5
H
4
þ 5H, Cp), 4.50 (m, 2H, C
5
H
4
), 7.33e7.46
), 68.95
5 4
H ), 84.67, 89.69 (C^C),
13
3.3. Reaction of phenylacetylene (Ia) with anysole
0
0
(
(
1
(
AA BB -system, 4H, C
CH, C ), 69.96 (CH, C
21.67 (Cipso, C
CH, C
weak (C^C).
6
H
4
); C NMR: 64.75 (Cipso, C
), 71.40 (CH, C
5 4
H
5
H
4
5
H
5
A mixture of anisole (2.5 ml; 2.49 g; 23 mmol), dry dichloro-
methane (4.5 ml), glacial acetic acid (23 ml), anhydrous FeCl
6
4
H ), 122.88 (Cipso, C
6
H
4
), 131.48 (CH, C
6
H
4
), 132.76
þ
ꢁ1
3
6
4
H ); cf. Ref. [9]. LDI: M 364, 366. IR: 2220, 2235 (shld) cm
,
(
(
(
2
0.46 g; 2.83 mmol), anhydrous FeCl (0.36 g; 2.83 mmol), copper
II) acetate monohydrate (0.35 g; 1.75 mmol) and phenylacetylene
1.25 ml; 1.16 g; 11.35 mmol) was stirred for 1 h at ambient
3
.2.2. 1-Ferrocenyl-2-trimethylsilylacetylene (IIc)
Reaction was carried out as specified in Section 3.1.1.
Ferrocene and trimethylsilylacetylene afforded IIc (0.474 g; 56%),
temperature, then for 1.5 h under reflux and cooled to ambient
temperature. Additional portions of copper(II) acetate mono-
hydrate (0.78 g; 3.88 mmol) and phenylacetylene (1.25 ml; 1.16 g;
ꢀ
ꢀ
m. p. 53.5e55 (from methanol), cf. Ref. [5]: m. p. 53.5e54.5 .
1
1.35 mmol) were added to the reaction mixture and stirring
1
H NMR: 0.21 (s, 9H, SiMe
3
), 4.18 (m), 4.19 (s, 2H, C
); C NMR: 0.23 (SiMe ), 64.97 (Cipso, C
), 70.21 (CH, C ), 71.80 (CH, C ), 90.52, 104.18
C^C), cf. Ref. [6]. IR: 2165, 2185 (shoulder) cm , strong (C^C).
5
H
4
and 5H,
was continued for 24 h.
13
Cp), 4.43 (m, 2H, C
8.78 (CH, C
(
5
H
4
3
5 4
H
),
Copper phenylacetylenide formed in the reaction was removed
from the resulting mixture by suction filtration and washed with
dichloromethane. Combined organic solution was poured into
solution of EDTA disodium salt dihydrate (3.0 g) in water (100 ml).
Organic layer was separated, water layer was extracted with
dichloromethane. Combined solution in dichloromethane was
6
5
H
4
H
5 5
5 4
H
ꢁ
1
3.2.3. 3-Ferrocenyl-2-propynole (IId)
Reaction was carried out as specified in Section 3.1.1. Ferrocene
ꢀ
and propargyl alcohol afforded IId (0.339 g; 47%), m. p. 84e85
recrystallized from heptane). Calculated for C13
H 5.04%. Found: C 65.12, H 5.18%.
2 4
washed with water, dried over Na SO and filtered. Solvent was
(
H12FeO: C 65.04,
removed on water bath using effective deflegmator. Gas chroma-
tography analysis of the residue detected 2.26 g (91%) of recovered
anisole. Non-reacted anisole and Ia were removed in vacuo.
From the residue obtained after distillation were isolated
1
H NMR: 1.84 (broad, 1H, OH), 4.08 (m), 4.10 (s, 2H, C
5
H
4
and 5H,
); C NMR: 51.64 (CH ),
), 69.85 (CH, C ), 71.36 (CH,
5 4
H ), 83.74, 84.36 (C^C), cf. Ref. [10]. IR: 3200e3400, broad (OH);
13
Cp), 4.28 (s), 4.30 (m, 2H, CH
2
and 2H, C
H
5 4
2
6
C
2
4.35 (Cipso, C
5
H
4
), 68.63 (CH, C
H
5 4
5 5
H
2
-(1-phenylvinyl)anisole IIIa (0.05 g; 1%) and 4-(1-phenylvinyl)
anisole IIIb (0.15 g; 3%), using column chromatography on silica gel
ꢁ
1
220, 2247 cm , weak (C^C).
2
(petroleum etherebenzene 1:1 mixture as eluent).
3
.2.4. 3-Ferrocenyl-1,1-dimethyl-2-propynole (IIe)
Reaction was carried out as specified in Section 3.1.1. Ferrocene
3
.3.1. Spectral data for IIIa
1
2
H NMR: 3.65 (s, 3H, CH
3
), 5.34 (d, J ¼ 1 Hz (1H, HeC])), 5.75
and 1,1-dimethyl-2-propynole afforded IIe (0.354 g; 44%), m. p.
9
6
2
(
1
d, J ¼ 1 Hz (1H, HeC])), 6.91e6.94 (m, 1H, C
6 4
H ), 6.98e7.02 (m,
ꢀ
3e94 (recrystallized from heptane). Calculated for C15
H
16FeO: C
13
H, Ph), 7.25e7.36 (m, 3H, C
), 114.06 (Cipso
), 126.34 (CH, Ph), 127.25 (CH, Ph), 127.99 (CH, Ph), 128.96 (CH,
H
6 4
and 4H Ph); C NMR: 55.57 (CH
3
),
7.19, H 6.01%. Found: C 67.47, H 6.21%.
1
111.21 (CH, C
C
C
H
6 4
C
6
H
4
eC ), 115.34 (¼CH ), 120.58 (CH,
2
H NMR: 1.58 (s, 6H, Me
and 5H, Cp), 4.38 (m, 2H, C
4.73 (Cipso, C ), 65.56 (CMe OH), 68.44 (CH, C
), 71.22 (CH, C ), 80.36, 90.20 (C^C). IR: 3200e3400,
broad (OH); 2230, 2250 cm , weak (C^C), cf. Ref. [11].
2
), 2.43 (broad, 1H, OH), 4.16 (m), 4.18
6
H
H
4
13
(
s, 2H, C
5
H
4
H
5 4
); C NMR: 31.60 (Me
2
),
), 69.81
6
4
), 131.23 (CH, C
H
6 4
), 146.97 (Cipso, Ph), 157.07 (C, ]C), 169.99
6
5
H
4
2
5 4
H
þ
(C
ipso, C
6
4
H eO), cf. Ref. [18]; M 210.
(
CH, C
5
H
5
5 4
H
ꢁ
1
3.3.2. Spectral data for IIIb
1
2
H NMR: 3.84 (s, 3H, CH
3
), 5.38 (d, J ¼ 1 Hz (1H, HeC])), 5.42
3
.2.5. 2-Ferrocenylacetylene (IIf)
Acetylene from a tank was purified by passing subsequently
2
(
d, J ¼ 1 Hz (1H, HeC])), 6.88e6.90 (m, 2H, Ph), 7.29e7.36 (m, 3H,
13
Ph and 4H AA’BB’, C
6
H
4
); C NMR: 55.26 (CH
3
), 112.91 (¼CH
2
),
through condenser cooled with acetone-dry ice mixture, concen-
trated sulfuric acid and glass wool.
1
1
(
13.50 (CH, C
29.37 (CH, C
C, ]C), 159.31 (Cipso, C
6 4
H ), 127.62 (CH, Ph), 128.10 (CH, Ph), 128.29 (CH, Ph),
H
6 4
), 133.96 (Cipso, C
H
6 4
eC), 141.79 (Cipso, Ph), 149.49
eO), cf. Ref. [19]; M 210.
Reagents and solvents were mixed in the following order:
ferrocene (0.558 g; 3 mmol), dry dichloromethane (2.6 ml), glacial
acetic acid (13 ml), anhydrous iron trichloride (0.122 g; 0.75 mmol),
copper(II) acetate monohydrate (0.10 g; 0.5 mmol). Purified acet-
ylene was bubbled through this mixture with stirring during 1 h at
ambient temperature, then for 1.5 h through refluxing mixture.
Reaction mixture was cooled to ambient temperature. Additional
portion of copper(II) acetate monohydrate (0.20 g; 1.0 mmol) was
added and stirring with bubbling of acetylene was continued for
þ
6
H
4
Acknowledgement
The research was supported by the Russian Foundation for Basic
Research, Grant # 08-03-00920-a.
2
19.5 h.
Yields are given based on Ia introduced in the reaction.

472
V.P. Dyadchenko et al. / Journal of Organometallic Chemistry 696 (2011) 468e472
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