Formation of acetylenic compounds and ring transformations of 3-alkyl-3-ferrocenylcyclopropenes in the reaction with 1,3-diphenylisobenzofuran

Article abstract of DOI:10.1016/S0022-328X(97)00670-0

The reaction of 3-ferrocenyl-3-methylcyclopropene with 1,3-diphenylisobenzofuran leads to the formation of exo- and endo-1,4-epoxy-2-ethynyl-2-ferrocenyl-1,4-diphenyltetralines as the main products in addition to the isomeric Diels-Alder exo-adducts. At the same time, 3-tert-butyl- and 3-(1-adamantyl)-3-ferrocenylcyclopropenes form the endo- and exo-adducts of 3-alkyl-1,2-(1-propene-1,3-diyl)ferrocene. The structures of the acetylenic compounds and of the adduct containing a ^tBu-substituent are established by X-ray structural analysis. A possible reaction pathway via intermediate zwitter-ion is discussed.

Full text of DOI:10.1016/S0022-328X(97)00670-0

Journal of Organometallic Chemistry 559 (1998) 1–10
Formation of acetylenic compounds and ring transformations of
3-alkyl-3-ferrocenylcyclopropenes in the reaction with
1,3-diphenylisobenzofuran
Elena I. Klimova a,c,*, Lena Ru´ız Ram´ırez a, Rafael Moreno Esparza a,
Tatiana Klimova Berestneva a, Marcos Martinez Garc´ıa b, Natalya N. Meleshonkova c,
Andrei V. Churakov c
a Uni6ersidad Nacional Auto´noma de Me´xico, Facultad de Qu´ımica, Circuito Interior, Cd. Uni6ersitaria, Coyoaca´n, CP 04510,
Me´xico D.F., Mexico
b Uni6ersidad Nacional Auto´noma de Me´xico, Instituto de Qu´ımica, Circuito Exterior, Cd. Uni6ersitaria, Coyoacan, CP 04510,
Me´xico D.F., Mexico
c Moscow State Uni6ersity M.V. Lomonoso6, Chemistry Department, Vorobjo6y Gory, 119899, Moscow, Russia
Received 20 June 1997
Abstract
The reaction of 3-ferrocenyl-3-methylcyclopropene with 1,3-diphenylisobenzofuran leads to the formation of exo- and
endo-1,4-epoxy-2-ethynyl-2-ferrocenyl-1,4-diphenyltetralines as the main products in addition to the isomeric Diels–Alder
exo-adducts. At the same time, 3-tert-butyl- and 3-(1-adamantyl)-3-ferrocenylcyclopropenes form the endo- and exo-adducts of
t
3-alkyl-1,2-(1-propene-1,3-diyl)ferrocene. The structures of the acetylenic compounds and of the adduct containing a Bu-sub-
stituent are established by X-ray structural analysis. A possible reaction pathway via intermediate zwitter-ion is discussed. © 1998
Elsevier Science S.A. All rights reserved.
Keywords: Iron; Ferrocene; Cyclopropene; Three-membered ring opening; Zwitter-ion; X-ray analysis
1. Introduction
We have also noted that all our attempts to iso-
late the expected product of a regular [4+2]-cy-
In previous papers [1,2], we reported the synthesis of
3-ferrocenyl-3-methylcyclopropene 1 and the three-
membered ring opening under the action of superacids:
cloaddition
diphenylisobenzofuran
clopropene 1, 3-ferrocenyl-3-phenylcyclopropene 4 re-
acts with diphenylisobenzofuran to give the
expected product of stereospecific [4+2]-cycloaddi-
tion together with 3-ferrocenylindene as a
of
cyclopropene
1
to
1,3-
3
failed. Contrary to cy-
3
5
6
product of an intramolecular transformation of 4
[3,4]. 3-Ferrocenylindene 6 was also obtained by pro-
tonation of cyclopropene 4 with superacids, followed
by treatment of the reaction mixture with N,N-
dimethylaniline:
* Corresponding author. Fax: +52
5
6225366; e-mail:
klimova@servidor.unam.mx
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(97)00670-0

2
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
The mechanism of the three-membered ring opening
tion of 1a with zinc powder gives significant amounts of
by-products (the yield of 1-ferrocenyl-1-methylcyclo-
propane being as high as 20% [1]), the reduction with
tBuOK/DMSO is highly selective [5]:
in 4, caused by protonation, seems to be similar to that
observed for ferrocenylmethylcyclopropene 1, i.e. it
possesses a distinct ionic character:
The formation of the same product 6 in both thermal
and ionic processes is a sign of an easy cleavage of the
| C–C bonds in the 3-ferrocenyl substituted cyclo-
propenes and of the possibility to influence this cleav-
age with the second substituent at position 3 [3,4].
2. Results and discussion
One should note that such a reduction of gem-di-
bromocyclopropanes bearing either aliphatic or aro-
matic substituents has never been reported. We believe
that the most plausible explanation of the above reac-
tion is a one-electron reduction of 7a–c by the mixture
of tBuOK/DMSO followed by an H atom transfer from
the solvent. The high yield of monobromo derivatized
8a–c demonstrates a sufficient stability of the suggested
intermediate.
In a continuation of our investigations, we studied
the reaction of 3-alkyl-3-ferrocenylcyclopropenes 1a–c
with 1,3-diphenylisobenzofuran 3 in detail. We found
that the initial cyclopropenes 1a–c can be prepared
easily by reduction of the 2,2-dibromo-1-alkyl-1-ferro-
cenylcyclopropanes 7a–c into the Z-2-bromo-1-alkyl-1-
t
ferrocenylcyclopropanes 8a–c with BuOK in DMSO,
followed by dehydrobromination of 8a–c into the de-
sired cyclopropenes 1a–c using the same reagents. Both
8a–c and 1a–c are obtained in good yields. It should
be also noted that while the previously employed reduc-
Prolonged reflux of a mixture of 3-ferrocenyl-3-
methylcyclopropene 1a and 1,3-diphenylisobenzofuran
3 in benzene or toluene leads to four products: classical
Diels–Alder adducts (11a,b) and adducts 9, 10 and 13:

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
3
˚
Fig. 1. Crystal structure of 9. Selected bond lengths (A) and bond angles (°): C(1)–C(11) 1.503 (3); C(11)–C(12) 1.469 (3); C(12)–C(16) 1.174 (4);
C(11)–C(13) 1.564 (3); C(11)–C(12)–C(16) 179.1 (2); C(14)–O–C(15) 98.0 (2); C(13)–C(11)–C(14) 99.6 (2).
1
The above scheme shows the structure of compound
The H-NMR spectra of compounds 9 and 10 unex-
pectedly indicated the presence of both ethynyl and
aliphatic methylene groups (see Section 3, Experimental).
In order to establish the structure of 9 and 10 by an
independent method, we carried out an X-ray investiga-
tion of single crystals of these compounds obtained from
hexane solution. The structures of exo-1,4-epoxy-2-
ethynyl-2-ferrocenyl-1,4-diphenyltetraline 9 and its endo-
isomer 10 are shown in Figs. 1 and 2, respectively.
In our viewpoint, the formation of adducts 9 and 10
in the reaction of 1a with 3 is the result of a thermal
heterolysis of a | C–C bond in the initial cyclopropene
1. One of the possible mechanisms is shown below:
13, which is obtained in minor quantities. This structure
is assigned to 13 on the basis of H-NMR spectral data
(see Experimental part). The formation of adducts with
1
similar structure will be discussed below.
1
The H-NMR spectra of compounds 11a,b contain
two signals of the protons of the methyl group with
intensity ratio 2:1. These signals prove the formation of
two isomeric compounds 11a and 11b (see Section 3,
Experimental).
1
The analysis of the H-NMR spectral parameters of
the methyl and ferrocenyl groups allows one to suggest
the existence of a three-membered ring with an exo-
configuration. The absence of a screening effect of the
o-phenylene ring on the methyl and ferrocenyl groups
(typical of endo-adducts [6,7]) also confirms the sug-
gested structure. The comparison of the chemical shifts
of the protons of the CH3 groups of the adducts 11a
and 11b with those in analogous compounds [4,6,7]
allows us to suggest that the adduct 11a formed in a
higher yield is 3-anti-ferrocenyl-3-syn-methyl-1,5-dip-
henyl-6,7-benzo-8-oxa-exo-tricyclo[3.2.1.02.4]oct-6-ene,
and 11b is 3-syn-ferrocenyl-3-anti-methyl-1,5-diphenyl-
6,7-benzo-8-oxa-ex o-tricyclo[3.2.1.02.4]oct-6-ene:
Examples of similar cleavage of the single C–C
bonds in carbocycles have been described previously for
compounds of the 1,2,3-triferrocenylcyclopropene [9–
11] and 3-ferrocenyl-3-phenylcyclopropene [3,4] series.
In solution and under various reaction conditions, these
compounds undergo ring opening followed by recy-
clization to give new condensed carbocyclic systems
with alkylated ferrocenyl and/or aryl fragments.
In our opinion, this ring opening is due to the
thermal heterolysis of 3-ferrocenyl-3-methylcyclo-
propene 1a, which results in the formation of an inter-
mediate 12a. This intermediate is easily deprotonated
into the structure 12b, as it is well known for h-ferro-
cenyl-h-methyl-carbocations [12–17], with subsequent
elimination of a hydride ion.
1,3-Diphenylisobenzofuran is a proton and hydride
ion acceptor. We observed in the reaction products the

4
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
presence of 1,3-dihydro-1,3-diphenylisobenzofurane 15
as a mixture of cis and trans isomers, ~1:1. The final
product of the thermal heterolysis should be 2-ferro-
cenylbut-1-en-3-yne 12c, which forms the Diels–Alder
adducts 9 and 10 with diphenylisobenzofuran 3. As
follows from the reaction mechanism presented above,
the methylene group in 12c is formed from the methyl
group of the initial cyclopropene 1a.
tons, of alkyl and phenyl fragments. The ratios 16a:
16b and 17a:17b between the isomers is approximately
3:1:
In order to verify our conclusions, we synthesized the
deuterium analogues of ferrocenylmethylcyclopropanes
7-D, 8-D and of cyclopropene 1-D:
The percentage of the isotopomer in 1-D is 92%
according to the H-NMR spectral data (see Table 1).
The adducts 9-D, 10-D and 11-D a,b were prepared
from the cyclopropene 1-D:
The isomer adducts were separated by thin layer
chromatography on SiO2. The structure of the 16a
adduct was established by X-ray analysis. The general
view of the molecule of 1,7-diphenyl-3,4-(3-tert-butyl-
1
No doublets for the protons of the methylene groups
in the H-NMR spectra of compounds 9-D and 10-D
ferroceno)-8,9-benzo-10-oxatricyclo[5.2.1.02.4]deca-3,8-
diene 16a is shown in Fig. 3. The data of X-ray
diffraction analysis of compound 16a indicate that the
1
were observed (see Table 1). However, we observed
singlets for the protons of the acetylenic fragments.
These results support our previous conclusion that the
methylene group originates from the methyl group of
the initial cyclopropene 1a.
1
obtained adduct has an endo-structure. The H- and
13C-NMR data allow to assign to compound 17a an
endo-structure and to compounds 13, 16b and 17b an
exo-structure.
Further we studied the interaction of 3-tert-butyl-
and 3-(1-adamantyl)-3-ferrocenylcyclopropenes 1b and
1c with 1,3-diphenylisobenzofuran 3. Unlike to the
It is obvious that this is possible only if the small
tricycle in the initial cyclopropenes 1b and 1c is opened
according to the possible reaction mechanism given
above. The intermediates 18a,b cannot be deproto-
nated. During the reaction they undergo intramolecular
transformations, which include:
1. Rearrangement of the h-ferrocenylcarbocation
centre with migration of the bulky substituent R
to position 3 of the C5H4-group of the ferro-
cenyl;
t
methyl group, the bulky, tertiary Bu and 1Ad sub-
stituents cannot be deprotonated under the applied
reaction conditions. That is why we did not observe the
classical Diels–Alder adducts 11-tBu and 11-1Ad in the
reaction products. According to 1H- and 13C-NMR
spectroscopic data, compounds 16a,b and 17a,b (see
Section 3, Experimental) contain 1,2,3-trisubstituted cy-
clopentadiene cycles in ferrocenes. The spectroscopic
data also indicate the presence of four aliphatic pro-
2. Alkylation of the C5H4-group in position 2:

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
5

6
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
The yield of compounds 21a and 21b was up to 30%.
Their structure was established by elemental analysis
1
and from H-NMR spectroscopic data (see Section 3,
Experimental).
In such a way we could confirm experimentally the
opening of the small cycle in 3-alkyl-3-ferrocenylcyclo-
propenes 1a–c and the formation of a carbene interme-
diate. The further chemical transformations of the
intermediate carbene depend both on the nature of the
alkyl substituent and on the type of compound interact-
ing with the ferrocenylcyclopropanes.
3. Experimental section
1
The H- and 13C-NMR spectra were recorded on a
‘Gemini 200 Varian’ spectrometer in CDCl3, with
Me4Si as the internal standard. All reactions were per-
formed in an atmosphere of dry argon.
3.1. 2,2-dibromo-1-alkyl-1-ferrocenylcyclopropanes
7a–c
˚
Fig. 2. Crystal structure of 10. Selected bond lengths (A) and bond
angles (°): C(1)–C(11) 1.521 (3); C(11)–C(12) 1.471 (3); C(12)–C(16)
1.178 (3); C(11)–C(13) 1.565 (3); C(11)–C(12)–C(16) 178.4 (2);
C(14)–O–C(15) 98.3 (1); C(13)–C(11)–C(14) 99.6 (2).
Dibromides 7a–c were prepared as reported earlier
[18] from alkenylferrocenes: 7a—orange crystals, yield
78%, m.p. 91°C [19]; 7b—orange crystals, yield 72%,
m.p. 127°C [19]; 7c—orange crystals, yield 74%, m.p.
These two processes are well known in the chemistry
of ferrocenylcarbocations and ferrocenylallylcations
[21–24]. We observe for the first time the simultaneous
proceeding of the two transformations. As a result, the
intermediate 3-alkyl-1,2-(1-propene-1,3-diyl)ferrocenes
20a,b are formed, which then convert to the adducts
16a,b and 17a,b.
We could not observe in the reaction products the
compounds 20a,b. However, we registered compounds
12a and 18a using as a trap diphenylacetylene:
1
75–76°C; H-NMR, l: 1.45, 1.74, 1.85, 2.40 (15H, m,
Ad), 4.08 (5H, s, C5H5), 4.09 (2H, m, C5H4), 4.12 (1H,
m, C5H4), 4.32 (1H, m, C5H4), 1.58 (1H, d, J=7.2 Hz),
2.81 (1H, d, J=7.2 Hz); Anal. Calcd. for C23H26Br2Fe,
%: C, 53.29; H, 5.06; Br, 30.87; Fe, 10.78; Found: C,
53.42; H, 5.21; Br, 21.03; Fe, 10.82.
3.2. Z-2-bromo-1-alkyl-1-ferrocenylcyclopropanes 8a–c
Dibromides 7a–c (1 mmol) were added to a solution
t
of BuOK (1.3 mmol) in 25 ml of absolute DMSO and
the mixture was stirred for 3–4 h. Then, 50 ml of
benzene and 30 ml of water were added to the resulting
mixture. The organic layer was separated, washed with
water, and concentrated. Monobromides 8a–c were

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
7
˚
Fig. 3. Crystal structure of 16a. Selected bond lengths (A) and bond angles (°): C(10)–C(16) 1.502 (4); C(15)–C(17) 1.557 (4); C(6)–C(10) 1.422
(4); C(6)–C(15) 1.511 (4); C(16)–C(17) 1.584 (4); C(10)–C(16)–C(15) 111.5 (3); C(6)–C(10)–C(16) 112.8 (2); C(6)–C(15)–C(17) 103.8 (2);
C(10)–C(16)–C(17) 102.8 (2); C(15)–C(17)–C(16) 109.0 (2).
isolated by chromatography on Al2O3 (III grade) using
hexane as eluent.
8a [5]—orange oil (yield 72%, Rf=0.74); H-NMR,
C5H4); Anal. Calcd. for C23H27BrFe, %: C, 62.89; H,
6.20; Br, 18.19; Fe, 12.72. Found: C, 63.10; H, 6.04; Br,
18.27; Fe, 12.93.
1
l: 1.36 (1H, dd, J=8.1, 5.6 Hz), 1.53 (3H, s), 1.74 (1H,
t, J=5.6 Hz), 3.12 (1H, dd, J=8.1, 5.6 Hz), 4.06 (5H,
s, C5H5), 4.25–3.85 (4H, m, C5H4); Anal. Calcd. for
C14H15BrFe, %: C, 52.71; H, 4.74; Br, 25.06; Fe, 17.50.
Found: C, 52.94; H, 4.61; Br, 24.95; Fe, 17.72.
8b—yellow cristals, yield 74%, m.p. 54–55°C, 1H-
NMR, l: 0.76 (9H, s), 1.39 (1H, dd, J=8.5, 5.68 Hz),
1.71 (1H, t, J=5.68 Hz), 3.35 (1H, dd, J=8.5, 5.68
Hz), 4.13 (5H, s, C5H5), 4.10 (2H, m, C5H4); 4.15 (1H,
m, C5H4); 4.19 (1H, m, C5H4); 13C-NMR, l: 20.36
(CH2), 26.15 (CH), 27.88 (CH3), 31.31, 33.68 (C), 65.30,
66.14, 71.19 (C5H4), 69.57 (C5H5), 93.22 (Cquat Fc);
Anal. Calcd. for C17H21BrFe, %: C, 56.54; H, 5.86; Br,
22.13; Fe, 15.47. Found: C, 56.29; H, 6.03; Br, 21.96;
Fe, 15.71.
3.3. 3-alkyl-3-ferrocenylcyclopropenes 1a–c
t
A mixture of BuOK (1.3 mmol) and monobromides
8a–c (1 mmol) in 25 ml of DMSO was stirred at room
temperature for 10 h. The reaction mixture was treated
as described above to give the cyclopropenes 1a–c:
1a—orange oil (yield 68%) [5]. Compound 1-D was
synthesized from 7-D following a method reported ear-
lier [5].
1
1b—yellow crystals, yield 74%, m.p. 39–40°C, H-
NMR, l: 0.70 (9H, s), 4.12 (5H, s, C5H5), 4.08 (2H, m,
C5H4); 4.10 (2H, m, C5H4); 7.35 (2H, s, CHꢀCH);
13C-NMR, l: 29.73 (CH3), 31.92, 34.53 (C), 68.60,
66.05 (C5H4), 68.12 (C5H5), 99.53 (Cquat Fc), 116.19
(CHꢀCH); Anal. Calcd. for C17H20Fe, %: C, 72.87; H,
7.19; Fe, 19.94. Found: C, 72.62; H, 6.94; Fe, 20.23.
1
8c—yellow cristals, yield 76%, m.p. 106–107°C, H-
NMR, l: 1.44 (1H, dd, J=8.5, 5.6 Hz), 1.69 (1H, t,
J=5.6 Hz), 1.22 (6H, m), 1.55 (6H, m), 1.89 (3H, m,
Ad), 3.40 (1H, dd, J=8.5, 5.6 Hz), 4.12 (5H, s, C5H5),
4.10 (1H, m, C5H4); 4.11 (1H, m, C5H4); 4.22 (2H, m,
1
1c—yellow crystals, yield 71%, m.p. 109–110°C, H-
NMR, l: 1.20–1.96 (15H, m, Ad), 4.02 (5H, s, C5H5),
3.97–4.01 (4H, m, C5H4); 7.42 (2H, s, CHꢀCH); 13C-

8
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
NMR, l: 27.80, 29.98 (CH2), 33.80, 35.60(CH), 32.40,
30.01(C), 68.63, 65.79 (C5H4), 68.06 (C5H5), 98.12
(Cquat Fc), 118.20 (CHꢀCH); Anal. Calcd. for C23H26Fe,
%: C, 77.10; H, 7.31; Fe, 15.59. Found: C, 77.21; H,
7.37; Fe, 15.28.
mately 20 h. The following products were isolated:
0.025 g as a mixture of 3 and 15a,b (15a:15b, ~1:1,
Rf=0.76) [8]; 0.02 g (8%) 11a,b (~2:1, Rf=0.60, m.p.
209–211°C); 0.062 g (25%) 9 (Rf=0.32, m.p. 195–
196°C), and 0.11 g (44%) 10 (Rf=0.28, m.p. 204–
205°C) and 0.008 g (~3.1%) 13 (Rf=0.45, m.p.
180–182°C).
3.4. Interaction of 3-alkyl-3-ferrocenylcyclopropenes
1a–c with 1,3-diphenylisobenzofuran 3
3.5. Reaction of cyclopropene 1b with
1,3-diphenylisobenzofuran 3
3.4.1. A
A mixture of cyclopropene 1a (0.12 g, 0.5 mmol) and
isobenzofuran 3 (0.27 g, 1 mmol) in 50 ml of dry
benzene was refluxed for 60 h until the disappearance
of the initial cyclopropene 1a (TLC). Following re-
moval of the solvent, the residue was subjected to
preparative TLC on silica gel in a 2:1 light petroleum–
benzene mixture. This resulted in:
0.02 g as a mixture of 3 and 1,3-dihydro-1,3-
diphenylisobenzofuran 15a,b (cis-/trans-, ~1:1, Rf=
0.75), 1H-NMR, l: 6.25 (CH, s), 6.51 (CH, s),
6.88–7.80 (m, C6H5, C6H4) [8], 0.03 g (12%) of a
mixture of Diels–Alder adducts 11a,b (~2:1, Rf=0.6,
m.p. 209–211°C); 1H-NMR, l: 1.50 s, 1.71 s (3H,
~2:1), 1.93 (2H, s), 4.14 (5H, s, C5H5), 4.05 (4H, m,
C5H4), 7.06, 7.12, 7.57, 7.70, 7.76 (14H, m); Anal.
Calcd. for C34H28FeO, %: C, 80.32; H, 5.55; Fe, 10.98;
Found: C, 80.17; H, 5.73; Fe, 11.07.
0.05 g (20%) of exo-1,4-epoxy-2-ethynyl-2-ferrocenyl-
1,4-diphenyltetraline 9 (Rf=0.31, m.p. 195–196°C);
1H-NMR, l: 2.26 (1H, s), 2.87 (1H, d, J=11.7 Hz),
3.27 (1H, d, J=11.7 Hz), 4.09 (5H, s, C5H5), 4.12 (1H,
m, C5H4), 3.99 (1H, m, C5H4), 3.87 (1H, m, C5H4), 3.78
(1H, m, C5H4), 6.99–7.04, 7.16–7.21, 7.24–7.28, 7.36–
7.59, 7.63–7.83 (14H, m); Anal. Calcd. for C34H26FeO,
%: C, 80.64; H, 5.18; Fe, 11.03; Found: C, 80.78; H,
5.08; Fe, 10.83.
A similar procedure (see method B) applied to 1.14 g
(0.5 mmol) of 1b and 0.27 g (1 mmol) of 3 in 50 ml of
toluene (10 h) gave:
0.16 g (57%) of endo-1,7-diphenyl-3,4-(3-tert-butyl-
ferroceno)-8,9-benzo-10-oxatricyclo [5.2.1.02.4]deca-3,8-
1
diene 16a (Rf=0.29, m.p. 206–207°C); H-NMR, l:
0.96 (9H, s), 2.08 (1H, dd, J=15.1, 3.4 Hz), 2.96 (1H,
dd, J=15.1, 9.0 Hz), 3.67 (1H, d, J=2.15 Hz, C5H2),
3.98 (1H, d, J=2.15 Hz, C5H2), 4.01 (5H, s, C5H5),
4.19 (1H, td, J=9.0, 3.4 Hz), 4.37 (1H, d, J=9.0 Hz),
6.75–6.98, 7.35–7.70 (14H, m); 13C-NMR, l: 138.73,
138.90, 144.74, 146.45 (Cipso), 120.53, 120.72, 125.98,
126.27, 126.92, 126.98, 127.98, 128.08, 128.39, 128.41
(Ph), 69.97 (C5H5), 59.12, 66.79 (C5H2), 91.46, 91.55,
94.93 (Cquat Fc), 54.31, 56.48 (CH), 30.54 (CH2), 30.65
(CH3), 30.80, 91.40, 91.79 (C); Anal. Calcd. for
C37H34FeO, %: C, 80.72; H, 6.22; Fe, 10.15; Found: C,
80.98; H, 6.15; Fe, 9.91.
And 0.051 g (18%) of its exo-isomer 16b (Rf=0.37,
1
m.p. 228–229°C); H-NMR, l: 1.07 (9H, s), 2.25 (1H,
dd, J=15.5, 3.6 Hz), 2.76 (1H, dd, J=15.5, 8.6 Hz),
3.43 (1H, d, J=1.8 Hz, C5H2), 3.61 (1H, d, J=1.8 Hz,
C5H2), 3.94 (5H, s, C5H5), 3.85 (1H, td, J=8.6, 3.6
Hz), 4.12 (1H, d, J=8.6 Hz), 7.0–7.15, 7.20–7.70
(14H, m); Anal. Calcd. for C37H34FeO, %: C, 80.72; H,
6.22; Fe, 10.15; Found: C, 80.63; H, 6.41; Fe, 10.24.
0.095 g (38%) of its endo-isomer 10 (Rf=0.28, m.p.
1
204–205°C); H-NMR, l: 2.12 (1H, s), 2.85 (1H, d,
3.5.1. Reaction of cyclopropene 1c with
1,3-diphenylisobenzofuran 3
Analogously, a similar procedure applied to 0.18 g
(0.5 mmol) of 1c and 0.27 g (1 mmol) of 3 in 50 ml of
toluene (8 h) gave:
J=11.7 Hz), 3.35 (1H, d, J=11.7 Hz), 4.13 (5H, s,
C5H5), 4.48 (1H, m, C5H4), 4.13 (1H, m, C5H4), 3.86
(1H, m, C5H4), 2.46 (1H, m, C5H4), 6.87, 6.92, 7.02,
7.18, 7.36–7.59, 7.69–7.74 (14H, m); Anal. Calcd. for
C34H26FeO, %: C, 80.64; H, 5.18; Fe, 11.03; Found: C,
80.54; H, 5.27; Fe, 11.21.
0.17 g (54%) of endo-17a (Rf=0.31, m.p. 213–
214°C); 1H-NMR, l: 1.48–1.70 (12H, m, Ad), 1.92
(3H, m, Ad), 2.08 (1H, dd, J=15.1, 3.2 Hz), 2.95 (1H,
dd, J=15.1, 9.2 Hz), 3.67 (1H, d, J=2.4 Hz, C5H2),
3.97 (1H, d, J=2.4 Hz, C5H2), 4.03 (5H, s, C5H5), 4.22
(1H, td, J=9.2, 3.3 Hz), 4.37 (1H, d, J=9.2 Hz),
6.60–7.00, 7.40–7.80 (14H, m); 13C-NMR, l: 138.81,
139.11, 144.80, 147.12 (Cipso), 120.65, 120.78, 125.93,
126.30, 126.98, 127.64, 128.10, 128.23, 128.54, 128.67
(Ph), 69.43 (C5H5), 66.75, 67.51 (C5H2), 92.13, 92.28,
95.08 (Cquat Fc), 54.72, 56.70, 28.55, 28.63 (CH), 30.63,
35.73, 36.05 (CH2), 41.71, 91.58, 91.73 (C); Anal.
Calcd. for C43H40FeO, %: C, 82.16; H, 6.41; Fe, 8.88;
Found: C, 81.94; H, 6.68; Fe, 8.55;
And 0.007 g (~3%) of adduct 13 (Rf=0.44, m.p.
1
181–182°C); H-NMR, d: 1.60 (3H, s), 1.75 (1H, dd,
J=11.4, 4.2 Hz), 2.88 (1H, dd, J=11.4, 10.6 Hz), 4.14
(5H, s, C5H5), 4.13 (1H, d, J=1.8 Hz, C5H2), 4.17 (1H,
d, J=1.8 Hz, C5H2), 3.72 (1H, td, J=11.4, 4.2 Hz),
4.96 (1H, d, J=10.6 Hz), 6.95–7.20, 7.40–7.85 (14H,
m); Anal. Calcd. for C34H28FeO, %: C, 80.32; H, 5.55;
Fe, 10.98; Found: C, 80.47; H, 5.38; Fe, 10.73.
3.4.2. B
The reaction was carried in 50 ml of toluene instead
of benzene and the reaction time decreased to approxi-

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
9
Table 2
Crystal data, data collection and refinement parameters for 9, 10 and 16a
Data
9
10
16a
Empirical molecular formula
Formula weight
Colour; habit
FeC34H26
506.40
Yellow, prism
Triclinic
O
FeC34H26
506. 40
Yellow, prism
Triclinic
O
FeC37H34
550.49
Orange, prism
Triclinic
O
Crystal system
(
(
(
Space group
P1
10.609(6)
P1
P1
10.300(2)
˚
a (A)
9.639(11)
11.140(7)
12.054(6)
80.23(5)
87.27(8)
82.23(8)
1263.5(2.0)
2
˚
b (A)
11.440(13)
11.539(9)
73.60 (8)
82.0 8(6)
71. 80(7)
1274. 3(2.0)
11.623 (2)
13.465 (3)
102.3 8(1)
112. 36(1)
98. 30(1)
1409.8(6)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
V (A )
Z
2
2
Dcalc (g cm−3
F(000)
)
1.320
528
0.614
Mo Kh, 0.71069
Graphite
293
2B2UB60
1.33 1
528
0.618
Mo Kh, 0.71069
Graphite
293
2B2UB54
v
5446
1.297
580
0.563
Mo Kh, 0.71073
Highly oriented graphite crystal
298
3B2UB56
U/2U
7841
Absorption coefficient (mm−1
)
˚
Radiation, l (A)
Monochromator
Temperature, K
2U range (°)
Scan type
v
Total reflections
Unique reflections
Reflections with I\2s(I)
Rint
6834
6521
4627
0.012
5193
4458
0.016
6733
4530
0.035
Solution
Refinement method
SHELX-86
Full-matrix least-squares on F2
SHELX-86
SHELX-97
Number of parameters refined
Hydrogen atoms
R (obs. data)
430
Riding
0.045
431
389
Riding
0.0582
Riding
0.039
Weighting scheme
w
−1=s2(F)+0.001832F2
w
−1=s2(F)
w
−1=s2(F)+0.0008F2
+0.003679F2
Goodness-of-fit
Min/max residual electron density, eA
1.19
−0.473/0.760
0.93
−0.403 /0.307
1.077
−0.667/0.415
−3
˚
And 0.057 g (18%) of its exo-isomer 17b (Rf=0.40,
m.p. 245–247°C); 1H-NMR, l: 1.38–1.73 (12H, m,
Ad), 2.01 (3H, m, Ad), 2.18 (1H, dd, J=15.2, 3.3 Hz),
2.68 (1H, dd, J=15.2, 9.0 Hz), 3.38 (1H, d, J=2.1 Hz,
C5H2), 3.65 (1H, d, J=2.1 Hz, C5H2), 3.96 (5H, s,
C5H5), 3.87 (1H, td, J=9.0, 3.3 Hz), 4.25 (1H, d,
J=9.0 Hz), 6.98–7.80 (14H, m); Anal. Calcd. for
C43H40FeO, %: C, 82.16; H, 6.41; Fe, 8.88; Found: C,
82.35; H, 6.37; Fe, 8.92.
0.14 g (0.5 mmol) of 1b and 0.18 g (1 mmol) of
diphenylacetylene gave 0.07 g (30%) of 5-tert-butyl-1,2-
diphenyl-5-ferrocenylcyclopentadiene 21b (Rf=0.44,
1
m.p. 186–187°C); H-NMR, l: 0.86 (9H, s), 3.60 (1H,
m, C5H4), 4.02 (1H, m, C5H4), 4.05 (1H, m, C5H4), 4.15
(1H, m, C5H4), 4.11 (5H, s, C5H5), 6.69 (1H, d, J=5.4
Hz), 6.79 (1H, d, J=5.4 Hz), 6.84 (2H, m, Ph), 7.10–
7.20 (8H, m, Ph); Anal. Calcd. for C31H30Fe, %: C,
81.22; H, 6.60; Fe, 12.18; Found: C, 81.38; H, 6.46; Fe,
12.40.
3.5.2. Reaction of cyclopropene 1a and 1b with
diphenylacetylene
3.5.3. Crystal structure in6estigation
Analogously, a similar procedure applied to 0.12 g
(0.5 mmol) of 1a and to 0.18 g (1 mmol) of dipheny-
lacetylene gave 0.064 g (30%) of 1,2-diphenyl-5-ferro-
cenyl-5-methylcyclopentadiene 21a (Rf=0.42, m.p.
The data were collected on an Enraf–Nonius CAD4
diffractometer (compounds 9 and 10) and on a Siemens
P4/PC diffractometer (compound 16a). Crystal data,
data collection and refinement parameters are listed in
Table 2.
1
164–165.5°C); H-NMR, l: 1.97 (3H, s), 3.61 (1H, m,
C5H4), 4.01 (1H, m, C5H4), 4.12 (1H, m, C5H4), 4.14
(1H, m, C5H4), 4.10 (5H, s, C5H5), 6.70 (1H, d, J=5.6
Hz), 6.77 (1H, d, J=5.6 Hz), 6.90 (2H, m, Ph), 7.16
(8H, m, Ph); Anal. Calcd. for C28H24Fe, %: C, 80.78;
H, 5.81; Fe, 13.41; Found: C, 80.53; H, 5.97; Fe, 13.23.
3.5.4. Synthesis of deuterated compounds
The deuterated compounds were synthesized follow-
ing known methods [1,5,15,20]. Their 1H-NMR spectral

10
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 559 (1998) 1–10
Table 3
Meleshonkova, I.G. Bolesov, Izv. Akad. Nauk Ser. Khim. (1996)
652 (Russ. Chem. Bull. 45 (1996) 613 (English Translation).
[5] E.I. Klimova, N.N. Meleshonkova, V.N. Postnov, T.C. Alvarez,
L.J. Gomez, G.M. Martinez, Dokl. Akad. Nauk 344 (1995) 498.
[6] V.V. Plemenkov, Kh.Z. Giniyatov, Ya.Ya. Villem, N.V. Villem,
L.S Surmina, I.G. Bolesov, Dokl. Akad. Nauk SSSR. 254 (1980)
895.
[7] W. Welter, A. Hartmann, M. Regitz, Chem. Ber. 111 (1978)
3068.
[8] J.G. Smith, R.B. McCall, J. Org. Chem. 45 (1980) 3982.
[9] A.J. Fry, P.S. Jain, R.L. Krieger, I. Agranat, E. Aharon-Shalom,
J. Organomet. Chem. 214 (1981) 381.
FAB+ mass spectral data for compounds 1-D, 7-D, 8-D(E-, Z-), 9-D,
10-D, 11-Da,b, 13-D and 14-D
Compound
Formula
FW
m/z
1-D
7-D
8-D (E-, Z-)
9-D
10-D
11-D a,b
13-D
14-D
C14H11D3Fe
240.87
400.88
321.99
508.28
508.28
511.40
511.40
229.07
241
399
321
508
508
511
511
229
C14H11Br2D3Fe
C14H12BrD3Fe
C34H24D2FeO
C34H24D3FeO
C34H25D3FeO
C34H25D3FeO
C13H11D3Fe
[10] A.J. Fry, R.L. Krieger, I. Agranat, E. Aharon-Shalom, Tetrahe-
dron Lett. 32 (1976) 4803.
[11] I. Agranat, E. Aharon-Shalom, R.L. Krieger, W.O. Krug, Tetra-
hedron 35 (1979) 733.
[12] J.A. Connor, J.P. Leloyd, J. Chem. Soc. Perkin I (1973) 17.
[13] A.N. Nesmeyanov, B.A. Surkov, V.A. Sazonova, V.M. Kra-
marov, Dokl. Akad. Nauk SSSR 215 (1974) 1128.
[14] E.I. Klimova, A.N. Pushin, V.A. Sazonova, J. Organomet.
Chem. 270 (1984) 319.
data are listed in Table 1. FAB+-mass spectral data
(positive mode) are listed in Table 3.
[15] E.G. Perevalova, E.I. Klimova, V.V. Kruchkova, A.N. Pushin,
Zh. Obsch. Khim. 59 (1989) 873.
Acknowledgements
[16] A.N. Pushin, E.I. Klimova, V.A. Sazonova, Zh. Obsch. Khim.
57 (1987) 1102.
[17] E.G. Perevalova, Yu.T. Struchkov, E.I. Klimova, A.N. Pushin,
Yu.L. Slovokhotov, Metalloorg. Khim. 2 (1989) 1405.
[18] N.V. Bovin, L.S. Surmina, N.I. Yakushkina, I.G. Bolesov, Zh.
Org. Khim. 3 (1977) 1188.
Financial support from CONACyT (Mexico) is
gratefully acknowledged.
References
[19] W.M. Horspool, R.G. Sutherland, B.J. Thomson, J. Chem. Soc.
C. (1971) 1550.
[1] V.N. Postnov, E.I. Klimova, N.N. Meleshonkova, I.G. Bolesov,
Dokl. Akad. Nauk 339 (1994) 362.
[2] V.N. Postnov, E.I. Klimova, N.N. Meleshonkova, I.G. Bolesov,
Dokl. Akad. Nauk 339 (1994) 496.
[3] E.I. Klimova, N.N. Meleshonkova, V.N. Postnov, T.C. Alvarez,
L.J. Gomez, G.M. Martinez, Dokl. Akad. Nauk 344 (1995) 639.
[4] E.I. Klimova, T.C. Alvarez, G.M. Martinez, L.J. Gomez, N.N.
[20] G. Wittig, U. Schoellkopf, Org. Syn. 40 (1960) 66.
[21] T.S. Abram, W. Watts, J. Chem. Soc. Perkin Trans. I (1975) 116.
[22] T.D. Turbitt, W.E. Watts, Chem. Communs. (1972) 951.
[23] T.D. Turbitt, W.E. Watts, J. Chem. Soc. Perkin Trans. II (1974)
189.
[24] E.I. Klimova, A.N. Pushin, V.A. Sazonova, J. Organomet.
Chem. 270 (1984) 319.
.
.