Regioselectivity of alkylation of the naphthalene fragment in the opening of a small ring in 3-ferrocenyl-3-(1-naphthyl)cyclopropene, Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane, and 1-ferrocenyl-1-(1-naphthyl)cyclopropane

Article abstract of DOI:10.1016/S0022-328X(98)00755-4

The opening of a small ring in 3-ferrocenyl-3-(1-naphthyl)cyclopropene (thermolysis, action of HBF₄·Et₂O or CF₃SO₃H), Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane (action of AlCl₃), and in 1-ferrocenyl-1-(1-naphthyl)cyclopropane (action of Ph₃C⁺BF₄^-) is accompanied by the alkylation of only the naphthalene fragment giving rise to 1-ferrocenyl-9bH-benzo[e]indene or 1-ferrocenyl-3H-benzo[e]indene. This is connected with a 'non-bisecting' position of the naphthalene fragment relative to the three-membered cycle in the starting compounds. The compound 1-ferrocenyl-9bH-benzo[e]indene gives [4+2]-cycloadducts with N-phenyl(azodicarboximide) and N-phenylmaleimide. X-ray structural data are presented for 3-ferrocenyl-3-(1-naphthyl)cyclopropene and its adduct with 1,3-diphenylisobenzofuran, Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane, and 1-ferrocenyl-1-(1-naphthyl)cyclopropane.

Full text of DOI:10.1016/S0022-328X(98)00755-4

Journal of Organometallic Chemistry 566 (1998) 175–185
Regioselectivity of alkylation of the naphthalene fragment in the
opening of a small ring in 3-ferrocenyl-3-(1-naphthyl)cyclopropene,
Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane, and
1-ferrocenyl-1-(1-naphthyl)cyclopropane
Elena I. Klimova a,c,*, Marcos Mart´ınez Garc´ıa b, Tatiana Klimova a,
Cecilio Alvarez Toledano b, Alfredo Ruben Toscano b, Rafael Moreno Esparza a,
Lena Ru´ız Ram´ırez a
b Uni6ersidad Nacional Auto´noma de Me´xico, Facultad de Qu´ımica, CP 04510, Me´xico DF, Mexico
a Uni6ersidad Nacional Auto´noma de Me´xico, Instituto de Qu´ımica, CP 04510, Me´xico DF, Mexico
c M.V. Lomonoso6 Moscow State Uni6ersity, Department of Chemistry, Vorobjo6y Gory, 119899, Moscow, Russia
Received 26 March 1998
Abstract
The opening of a small ring in 3-ferrocenyl-3-(1-naphthyl)cyclopropene (thermolysis, action of HBF4 ·Et2O or CF3SO3H),
Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane (action of AlCl3), and in 1-ferrocenyl-1-(1-naphthyl)cyclopropane (action of
Ph3C+BF4−) is accompanied by the alkylation of only the naphthalene fragment giving rise to 1-ferrocenyl-9bH-benzo[e]indene
or 1-ferrocenyl-3H-benzo[e]indene. This is connected with a ‘non-bisecting’ position of the naphthalene fragment relative to the
three-membered cycle in the starting compounds. The compound 1-ferrocenyl-9bH-benzo[e]indene gives [4+2]-cycloadducts with
N-phenyl(azodicarboximide) and N-phenylmaleimide. X-ray structural data are presented for 3-ferrocenyl-3-(1-naph-
thyl)cyclopropene and its adduct with 1,3-diphenylisobenzofuran, Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane, and 1-fer-
rocenyl-1-(1-naphthyl)cyclopropane. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Ferrocene; Naphthalene; Cyclopropane; Cyclopropene; Alkylation; Opening of a three-membered ring; Carbocations;
Carbenoids; X-ray structural analysis; [4+2]-Cycloadducts
1. Introduction
ments [1]. The compound 3-ferrocenyl-3-phenylcyclo-
propene 1 at acid or thermal cleavage of the small ring
forms 3-ferrocenylindene 2 [2–4].
The introduction of a ferrocenyl substituent in posi-
tion 3 of the cyclopropene ring significantly changes the
properties of the latter. Some well known examples of
changes in the reaction properties of the small carbocycle
include the transformations of 1,2,3-triferrocenylcyclo-
propene [1], 3-ferrocenyl-3-phenylcyclopropene 1 [2–4]
and also of 3-tert-butyl- and 3-adamantyl-3-ferrocenyl-
cyclopropenes 2a,b [5]. In particular, 3-para-tolyl-1,2,3-
triferrocenylcyclopropene, even at 0°C, in a solution of
CHCl3, rearranges due to cleavage of the small ring,
followed by cyclization at the ferrocenyl and aryl frag-
In our opinion, the high regioselective intramolecular
alkylation of the phenyl substituent and not of the
ferrocenyl one, as normally observed for other ferrocenyl
compounds [1,6–8], should be related to the spatial
* Corresponding author. Fax: +52
klimova@servidor.unam.mx
5
6162217; e-mail:
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00755-4

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E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
structure of the cyclopropene compound 1 [4]. Accord-
ing to X-ray analysis data, the phenyl subsituent has a
‘non-bisecting’ position relative to the small ring, while
the ferrocenyl fragment has a ‘bisecting’ spatial orienta-
tion. Therefore, during the small ring cleavage, the
alkylation should take place at the substituent which has
a ‘non-bisecting’ orientation. However, if the ferrocenyl
substituent occupies a ‘non-bisecting’ position one
should expect that the alkylation will take place at the
ferrocenyl fragment. In the reaction of 3-alkyl-3-ferro-
cenylcyclopropenes 3a,b (the ferrocenyl fragment has a
‘non-bisecting’ position) with 1,3-diphenylisobenzo-
furan, the adduct 5a,b is formed from the intermediate
3-alkyl-1,2-(1-propene-1,3-diyl)ferrocene 4a,b [5].
Monocrystals of compounds 6, 7, and 9 necessary for
X-ray structural analysis were obtained by crystalliza-
tion from hexane. General views of these molecules are
shown in Fig. 1(Fig. 2a) and Fig. 3, respectively. The
X-ray analysis data indicate that all studied compounds
(cyclopropene 6, monobromide 7 and cyclopropane 9)
have identical conformations. This is probably caused by
sterical restrictions imposed on the rotation of the
geminal ferrocenyl and aryl substituents arround the
simple C–C bonds.
The principal elements in the structures of 6, 7, and
9 are the three-membered rings. The three-membered
ring in compound 6 is a triangle with an acute angle
The idea that regioselectivity in similar reactions
depends on the spatial orientation of the substituents
(the conformational structure of the molecules) is not
studied in detail and deserves further investigation.
extended towards C(11). The length of the CHꢀCH
˚
double bond (d=1.272(6) A) and the angle ꢀ at C(11)
is equal to 50.0(2)°. In compounds 7 and 9, the angles
at the carbon atoms C(1) and C(21), respectively, are
smaller than 60° (56.4 and 59.0°), C(2)–C(3) and C(22)–
C(23) bond lengths are shorter than the lengths of the
lateral bonds C(1)–C(2), C(1)–C(3), C(21)–C(22), and
C(21)–C(23). The angles of rotation of the ferrocene and
naphthalene fragments in the molecules under consider-
ation correspond to the ‘bisecting’ position of the former
and ‘non-bisecting’ position of the latter relative to the
small ring (Figs. 1, 2a and 3). X-ray analysis of mono-
bromide 7 revealed that the unit cell of monoclinic
2. Results and discussion
In a continuation of our investigations, we synthesized
crystalline 3-ferrocenyl-3-(1-naphthyl)cyclopropene 6,
Z-2-bromo-1-ferrocenyl-1-(1-naphthyl)cyclopropane 7,
and 1-ferrocenyl-1-(1-naphthyl)cyclopropane 9 starting
from 2,2-dibromo-1-ferrocenyl-1-(1-naphthyl)cyclopro-
pane 8 and studied their structures and some of their
chemical transformations.

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
177
˚
Fig. 1. Crystal structure of 6. Selected bond lengths (A): C11–C12=1.498(5); C11–C13=1.509(5); C12–C13=1.272(6); and selected bond angles
(°): C12–C11–C13=50.0(2); C13–C12–C11=65.4(3); C12–C13–C11=64.5(3).
crystals of this compound contains two molecules with
the bromine atoms close to each other (Fig. 2b). In all
the three compounds 6, 7, and 9, the Fe–C and C–C
bonds as well as the geometry of the ferrocene sand-
wich have normal parameters.
We found that in the Diels–Alder adduct 11 the
conformation of the fragment containing the small ring
is preserved: ferrocene occupies a ‘bisecting’ position
and naphthalene a ‘non-bisecting’ position.
thalene and ferrocene fragments in the adduct 11 (Fig.
4).
Not only was the adduct 11 isolated from the reac-
tion mixture but also Z-1-ferrocenyl-1-(1-naph-
thyl)propene-1. The fact that propene 12a is formed in
the reaction of 6 with 10 points to a possible opening of
the small ring in the thermal process. When the reaction
was carried out at a higher temperature (in boiling
m-xylene), the yields of both the adduct 11 and propene
1H- and 13C-NMR spectra of the adduct 11 corre-
spond to only one structural isomer, which attests to a
stereospecific [4+2]-cycloaddition. The structure of
compound 11 is established on the basis of X-ray data.
General view of this molecule is shown in Fig. 4. X-ray
data show that compound 11 has the structure of
exo-3-ferrocenyl-3-(1-naphthyl)-1,5-diphenyl-6,7-benzo-
8-oxatricyclo[3.2.1.02,4]oct-6-ene with a syn-orientation
of the naphthalene substituent. The non-equivalence of
the hydrogen atoms H(2) and H(4) in the 1H-NMR
spectrum and of the carbon atoms C(1) and C(5) in the
13C-NMR spectrum (see Section 4) can easily be ex-
plained by a mutual ‘anti’-orientation of the naph-
12a were lower. A product isolated from the reaction
mixture was identified as 1-ferrocenyl-9bH-ben-
zo[e]indene 13 on the basis of H-NMR spectral data [l
2.49 (s, 1 H, CH), 6.48 (d, 1 H, J=5.55 Hz), 6.80 (d, 1
H, J=5.55 Hz), plus signals for 9H of ferrocene and
6H of naphthalene fragments].
1

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E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
˚
Fig. 2. (a) Crystal structure of 7. Selected bond lengths (A): C1–C2=1.513(17); C1–C3=1.510(15); C2–C3=1.429(19); and selected bond angles
(°): C2–C1–C3=56.4(8); C1–C2–C3=61.7(8); C1–C3–C2=61.9(8). (b) Crystal packing of 7.
Benzoindene 13 was also obtained in a 63% yield
when cyclopropene 6 was boiled in m-xylene for 8 h:
613“5°C13+12a (14%)
Compound 13 forms [4+2]-cycloadducts 14 and 15
with N-phenyl(azodicarboximide) and N-phenyl-
maleimide, respectively.

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
179
˚
Fig. 3. Crystal structure of 9. Selected bond lengths (A): C21–C22=1.517(6); C21–C23=1.513(6); C22–C23=1.492(8); and selected bond angles
(°): C22–C21–C23=59.0(3); C21–C22–C23=60.4(3); C22–C23–C21=60.6(3).
The structures of the adducts 14 and 15 were estab-
The opening of a small ring in cyclopropene 6 with
superacid CF3SO3H gave mainly benzoindene 16 (ca.
64%) and the products of p-alkylation of N,N-dimethy-
laniline, 17a,b (ca. 11%).
It is believed that in this case the protonation of
cyclopropene 6 results in an intermediate cyclopropyl
cation 18, which undergoes smooth opening to give a
ferrocenylallylic cation 19 [2–4] stabilized by the fer-
rocene substituent.
1
lished on the basis of H- and 13C-NMR spectral data
(see Section 4). The fact that the signals for the protons
of the C5H4 group of the ferrocene fragment are shifted
downfield relative to the singlet for the protons of the
non-substituted cyclopentadienyl ring of ferrocene made
it possible to attribute 15 to the exo-type structure [2,6].
It has also been discovered that the three-membered
ring in cyclopropene 6 undergoes smooth opening under
the action of HBF4 ·Et2O. Following treatment of the
reaction mixture with N,N-dimethylaniline, Z- and E-1-
ferrocenyl-1-(1-naphthyl)prop-1-enes 12a and 12b (ca.
5:1, 1H-NMR data), 1-ferrocenyl-3H-benzo[e]indene 16,
and Z- and E-3-(p-dimethylaminophenyl)-1-ferrocenyl-
1-(1-naphthyl)prop-1-enes 17a and 17b (ca. 4:1, 1H-
NMR data) were isolated by TLC.

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E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
˚
Fig. 4. Crystal structure of 11. Selected bond lengths (A): C11–C12=1.519(6); C11–C13=1.532(6); C12–C13=1.513(6); and selected bond angles
(°): C12–C11–C13=59.5(3); C13–C12–C11=60.7(3); C12–C13–C11=59.8(3); C34–C11–C10=113.9(4); C34–C11–C12=121.7(4); C34–C11–C13
=
125.7(4).
The cation 19 then enters into intramolecular trans-
formations and alkylates the naphthalene (‘non-bisect-
ing’) substituent, it also alkylates N,N-dimethylaniline
by the less substituted carbenium center [9,10], and
undergoes reduction. Reduction of this type of ferro-
cenylallylic cations has previously been observed for
1-ferrocenyl-1-phenylallyl cation [4] and 3-ferrocenyl-
methylene-1,2,7,7-tetramethylbicyclo[2.2.1]hept-2-yl
cation [11,12], which is associated, in our opinion, with
the participation of the iron atom [13].
However, the reduction of 20, unlike that of cation
19, is stereospecific, this results in the Z-alkene 12a; the
intramolecular transformation of 20 gives 9bH-ben-
zo[e]indene 13, which differs in structure from 3H-ben-
zo[e]indene 16.
It has also been demonstrated that the small ring
is easily opened upon treatment of monobromo-
cyclopropane 7 with AlCl3 [4] and of cyclopro-
pane
9 with triphenylcarbenium tetrafluoroborate
[14,15].
The formation of compounds 12a and 13 in thermal
processes might occur due to heterolysis of one of the
|-bonds of the small ring [3,5]. The intermediate car-
benoid 20 is involved in intramolecular alkylation and
reduction analogous to those of the ferrocenylallylic
cation 19.
The opening of a small ring in 7 occurs as a re-
sult of detachment of a halide anion and genera-
tion of a cationic center in the cyclopropane ring
with subsequent (or simultaneous) opening of
the small ring and formation of an allylic cation
19.

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
181
Thus, 1-ferrocenyl-3H-benzo[e]indene 16 was isolated
4. Experimental
as the main reaction product (ca. 67%). The reaction of
cyclopropane 9 with triphenylcarbenium tetrafluorobo-
rate occurs in a more complex way. Ring-opening in 9
due to hydride detachment [14,15] and the formation of
the allylic cation 19 is only one of the processes that
occur:
The solvents were dried by standard methods and
distilled prior to use. Column chromatography was
carried out on Al2O3 (activity III according to Brock-
mann). Elemental analyses were carried out by the
Microanalytical laboratory of the Department of
Chemistry of the Moscow State University. 1H- and
13C-NMR spectra were registered in CDCl3 on a
Gemini 200 Varian spectrometer at 200 and 50 MHz
using Me4Si as the internal standard. The parameters
of the unit cell and the X-ray diffraction intensities
were recorded on Siemens P4/PC (compounds 6, 9 and
11) and Siemens P4 (compound 7) spectrometers (Table
1).
+
−
7+Ph C
“
[18]“[19]PhN(CH3)216 (23%)+17a,b (5%)
“
BF
3
4
−Ph CH
3
In addition, competitive opening of the three-mem-
bered ring occurs predominantly due to electrophilic
addition of Ph3C+ leading to cation 21. Its deprotona-
tion with N,N-dimethylaniline results in 1-ferrocenyl-
4,4,4-triphenyl-1-(1-naphthyl)but-1-ene 22 as a mixture
of two isomers 22a and 22b in a ratio of ca. 2:1
1
according to H-NMR data.
The major isomer 22a was isolated individually.
However, the configuration of compounds 22a and 22b
(Z- or -E) has not been established yet.
4.1. 2,2-Dibromo-1-ferrocenyl-1-(1-naphthyl)cyclo-
propane 8
Cyclopropane 8 was obtained by a standard proce-
dure [16] from 1-ferrocenyl-1-(1-naphthyl)ethylene in a
yield of 75%; orange crystals, m.p. 141–142°C. 1H-
NMR: l 2.46 (d, 1 H, CH2, J=8.0 Hz), 2.55 (d, 1H,
CH2, J=8.0 Hz), 3.95 (s, 5 H, C5H5), 3.63 (m, 1H),
3.98 (m, 1 H), 4.15 (m, 1H), 4.27 (m, 1H) (C5H4), 7.98,
8.05 (m, 7H, C10H7). 13C-NMR: l 35.63 (CH2), 38.60
(C), 66.10 (C), 68.79 (C5H5), 67.04, 68.09, 68.99, 71.16
(C5H4), 89.72 (Cipso Fc), 125.11, 125.84, 125.98, 127.39,
127.53, 128.26, 128.41 (CH), 129.44, 133.73, 138.75
(Cipso). Anal. Found: C, 54.25; H, 3.49; Br, 31.60; Fe,
11.04. C23H18Br2Fe. Calc.: C, 54.16; H, 3.56; Br, 31.33;
Fe, 10.95%.
3. Conclusion
Thus, the results of this study support our previous
conclusion [4] that the regioselectivity of intramolecular
transformations of 3-aryl-3-ferrocenylcyclopropenes 1
and 6 and 1-aryl-1-ferrocenylcyclopropanes 7 and 9 is
determined by spatial orientation of substituents in the
starting compounds. Aryl substituents that occupy a
‘non-bisecting’ position relative to the three-membered
ring undergo alkylation upon opening of the small ring
under various conditions. We did not observe in-
tramolecular cyclization involving the ferrocene frag-
ment, although such an intramolecular alkylation of a
k-ferrocenyl group (relative to the cationic or carbenoid
center) is well known. This seems to be connected with
the ‘bisecting’ orientation of the ferrocene fragment in
compounds under study.
4.2. Z-2-Bromo-1-ferrocenyl-1-(1-naphthyl)cyclo-
propane 7
A solution of EtMgCl (3.2 mmol) in ether and sev-
eral drops of (iPrO)4Ti were added to a solution of

182
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
Table 1
Crystal data, data collection and refinement parameters for 6, 7, 9 and 11
Data
6
7
9
11
Molecular formula
Formula weight (g mol−1
Crystal size (mm)
Color, habit
Temperature (K)
Crystal system
C23H18Fe
350.23
0.70×0.15×0.15
Orange, needle
298
C23H19BrFe
431.10
0.75×0.70×0.15
Yellow, plate
293
Monoclinic
P21/c
9.668(3)
27.143(4)
6.9920(10)
—
102.45(2)
—
1790.1(7)
4
1.600
3.076
C23H20Fe
352.24
0.70×0.24×0.16
Orange, prism
293
Monoclinic
P21/n
7.404(2)
18.980(3)
12.418(2)
90
98.30(2)
90
1726.8(6)
4
1.355
0.873
C43H32FeO
620.54
0.15×0.10×0.10
Orange, regular
298
)
Triclinic
Triclinic
(
(
Space group
P1
P1
˚
a (A)
7.508(1)
14.563(2)
15.995(2)
92.14(1)
102.95(1)
94.40(1)
1696.62(42)
2
7.765(2)
10.909(2)
18.967(3)
89.73(1)
85.47(1)
78.22(2)
1567.8(6)
2
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
V (A )
Z
Dcalc (g cm−3
)
1.355
0.887
712
1.314
0.515
648
v (mm−1
F(000)
)
872
736
Radiation
u (A)
Mo–Kh
0.71073
Mo–Kh
0.71073
Mo–Kh
0.71073
Mo–Kh
0.71073
˚
Monochromator
2q range (°)
Scan type
Reflections collected
Unique reflections
Rint
Highly oriented graphite crystal
3.0B2qB50.0
q/2q
7445
2.0B2qB50.0
2q-v
4351
3.97B2qB50.0
2q-v
3281
3034
0.0425
3.0B2qB46.0
q/2q
5490
4354
0.0672
5954
3158
0.0236
0.0494
Reflections with I\2|(I)
R1=0.0474,
wR2=0.0798
R1=0.0990,
wR2=0.0905
5904/0/469
R1=0.0657,
wR2=0.0849
R1=0.1420,
wR2=0.1621
3158/0/226
R1=0.0475, wR2=0.0928
R1=0.0637,
wR2=0.0757
R1=0.1707,
wR2=0.0932
4304/0/438
R indices (all data)
R1=0.0879, wR2=0.1093
3034/0/217
Data/restraints/parameters
Refinement method
Weighting scheme
Full-matrix least-squares on F2
w
−1=|2(F)
w
−1=|2(F)
w
−1=|2(F2o)+(0.0334P)2+0.4027P;
w
−1=|2(F)
+0.0008F2
0.944
+0.0050F2
0.95
where P=(F2o+2Fc2)/3
1.027
+0.0008F2
0.895
Goodness-of-fit
Min./max. residual electron density
−0.253/0.261
−1.28/0.95
−0.269/0.318
−0.293/0.284
−3
˚
(e A
)
Hydrogen atoms
R (observed data)
Solution
Riding
0.0474
SHELX-97
Riding
0.0657
Direct methods
Riding
0.0475
Direct methods (SIR92)
Riding
0.0637
SHELX-97
dibromide 8 (1.53 g, 3 mmol) in dry ether (50 ml). The
mixture was stirred at room temperature (r.t.) until the
dark brown color turned yellow, and then water (50 ml)
was added dropwise. The organic layer was separated,
the solvent was distilled off and the residue was chro-
matographed on Al2O3 (hexane as the eluent) to yield
1.04 g (80%) of monobromide 7, yellow crystals, m.p.
108–109°C. 1H-NMR: l 1.76 (dd, 1H, CH2, J=5.7, 6.6
Hz), 2.15 (dd, 1H, CH2, J=6.6, 8.4 Hz), 3.53 (dd, 1H,
CH2, J=5.7, 8.4 Hz), 4.08 (s, 5H, C5H5), 3.55 (m, 1H),
3.98 (m, 1H), 4.20 (m, 1H), 4.35 (m, 1H) (C5H4),
7.46–8.02 (m, 7H, C10H7). Anal. Found: C, 63.85; H,
4.58; Br, 18.68; Fe, 13.07. C23H19BrFe. Calc.: C, 64.07;
H, 4.44; Br, 18.54; Fe, 12.95%.
4.3. 1-Ferrocenyl-1(1-naphthyl)cyclopropane 9
The compound 1-ferrocenyl-1(1-naphthyl)cyclopro-
pane 9 was obtained analogously from dibromide 8
(1.53 g) and EtMgCl (6.2 mmol) in ether and (iPrO)4Ti
(1 ml). Yield 0.95 g (73%), yellow crystals, m.p. 118–
1
119°C. H-NMR: l 1.35 (m, 2H, CH2), 1.38 (m, 2H,
CH2), 3.71 (m, 2H), 3.93 (m, 2H) (C5H4), 4.11 (s, 5H,
C5H5), 7.40–8.26 (m, 7H, C10H7). 13C-NMR: l 19.40
(CH2), 19.44 (CH2), 37.15 (C), 66.60 (C5H4), 68.48
(C5H5), 69.56 (Cipso Fc), 125.34, 125.41, 125.43, 125.94,
127.37, 127.94, 128.42 (CH), 133.10, 133.82, 140.78
(Cipso). Anal. Found: C, 78.35; H, 5.94; Fe, 15.63.
C23H20Fe. Calc.: C, 78.42; H, 5.72; Fe, 15.85%.

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
183
4.4. 3-Ferrocenyl-3-(1-naphthyl)cyclopropene 6
(C5H4), 88.52, 88.54 (C-1, C-5), 95.86 (Cipso Fc), 118.98,
119.04, 123.39, 124.38, 125.03, 126.10, 126.27, 126.66,
126.85, 127.63, 127.74, 128.34 (CH), 132.05, 132.98,
134.78. 136.24, 138.08, 149.63, 150.35 (Cipso). Anal.
Found: C, 83.36; H, 5.04; Fe, 8.74. C43H32FeO. Calc.:
C, 83.22; H, 5.20; Fe, 9.00%.
t
A mixture of Z-7 (1.3 g, 3 mmol) and BuOK (4
mmol) in DMSO (30 ml) was stirred for 10 h at 20°C in
an atmosphere of dry argon. Benzene (100 ml) and
water (50 ml) was then added, the organic layer was
separated and washed with water. The solvent was
distilled in vacuo and the residue was chromatographed
on Al2O3 (hexane as the eluent). Eluted first was 3-ferro-
cenyl-3-(1-naphthyl)prop-1-ene (6a), (0.21 g, 20%), m.p.
103–104°C. 1H-NMR: l 4.11 (s, 5H, C5H5), 4.12 (d, 1H,
J=5.8 Hz), 3.75 (m, 2 H), 4.27 (m, 1H), 4.53 (m, 1H)
(C5H4), 4.80 (dd, 1H, CH2, J=1.20, 5.8 Hz), 5.28 (dd,
1H, CH2, J=1.20, 8.0 Hz), 5.96 (m, 1H, CHꢀ), 6.85,
7.30–7.60, 7.72–7.90 (m, 7H, C10H7). Anal. Found: C,
78.19; H, 5.93; Fe, 16.06. C23H20Fe. Calc.: C, 78.42; H,
5.72; Fe, 15.85%. Eluted second was cyclopropene 6,
yield 0.63 g (60%), yellow needles, m.p. 123–124°C.
1H-NMR: l 3.74 (m, 2 H), 3.96 (m, 2H) (C5H4), 4.15 (s,
5H, C5H5), 7.51 (s, 2H, CHꢀCH), 7.38–7.58, 7.70–7.80,
8.10–8.20 (m, 7H, C10H7). 13C-NMR: l 26.33 (C),
67.12, 67.94 (C5H4), 68.05 (C5H5), 98.73 (Cipso Fc),
113.48 (CHꢀCH), 125.42, 125.46, 125.49, 125.63,
125.92, 126.99, 128.51 (CH), 132.04, 133.99, 143.08
(Cipso). Anal. Found: C, 78.98; H, 5.26; Fe, 15.73.
C23H18Fe. Calc.: C, 78.87; H, 5.18; Fe, 15.95%.
(b) Analogously, compounds 6 (0.35 g) and 10 (0.56
g) were refluxed in m-xylene to give 0.024 g (7%) of
Z-12a, m.p. 119°C, 0.32 g (50%) of adduct 11, m.p.
265–267°C, and 0.07 g (20%) of indene 13, Rf 0.29,
1
pale-yellow crystals, m.p. 121–122°C. H-NMR: l 2.48
(s, 1H, CH), 4.18 (s, 5H, C5H5), 4.01 (m, 1H), 4.06 (m,
1H), 4.20 (m, 1H), 4.72 (m, 1H) (C5H4), 6.75 (d, 1H,
J=5.7 Hz), 6.81 (d, 1H, J=5.7 Hz), 7.33–7.46, 7.75–
7.81, 8.31–8.34 (m, 6H, C10H6). Anal. Found: C, 78.71;
H, 5.27; Fe, 16.23. C23H18Fe. Calc.: C, 78.87; H, 5.18;
Fe, 15.95%.
4.6. Thermolysis of
3-ferrocenyl-3-(1-naphthyl)cyclopropene 6
A solution of cyclopropene 6 (0.35 g, 1 mmol) in
m-xylene (50 ml) was refluxed for 6 h under dry argon.
The solvent was evaporated in vacuo and the residue
was chromatographed (TLC on silica gel, hexane–ben-
zene, 2:1) to yield 0.05 g (14%) of alkene 12a, m.p.
118–119°C, Rf 0.75, and 0.22 g (63%) of indene 13, m.p.
121–122°C, Rf 0.3.
4.5. Reaction of cyclopropene 6 with
1,3-diphenylisobenzofuran 10
4.7. Reaction of 1-ferrocenyl-9bH-benzo[e]indene 13
with N-phenyl(azodicarboximide)
(a) A mixture of cyclopropene 6 (0.35 g, 1 mmol) and
compound 10 (0.56 g, 2 mmol) in toluene (50 ml) was
refluxed until the starting compound 6 disappeared
(TLC control on Silufol plates in hexane). The solvent
was evaporated in vacuo and the residue was chro-
matographed (TLC on silica gel, hexane–benzene, 2:1)
to give compounds 12a and 11.
Z-1-Ferrocenyl-1-(1-naphthyl)prop-1-ene (12a), Rf
0.78, yield 0.042 g (10.2%), yellow crystals, m.p. 118–
119°C. 1H-NMR: l 1.42 (d, 3H, CH3, J=6.92 Hz), 4.08
(s, 5H, C5H5), 3.74 (m, 1H), 4.02 (m, 1H), 4.19 (m, 1H),
4.41 (m, 1H) (C5H4), 6.32 (q, 1H, CHꢀ, J=6.92 Hz),
7.31–7.60, 7.75–7.90 (m, 7H, C10H7). 13C-NMR: l
29.69 (CH3), 69.26 (C5H5), 64.79, 67.94, 68.05 (C5H4),
87.12 (Cipso Fc), 122.08 (CHꢀ), 125.35, 125.62, 125.66,
126.20, 126.74, 127.12, 128.15 (CH), 128.05 (C), 133.63,
137.01, 140.05 (Cipso). Anal. Found: C, 78.23; H, 5.88;
Fe, 15.69. C23H20Fe. Calc.: C, 78.43 (compound6a
78.42%); H, 5.72; Fe, 15.85%.
Portions of N-phenyl(azodicarboximide) (0.058 g)
were added at 20°C to a solution of indene 13 (0.12 g,
0.33 mmol) in dry benzene (10 ml) as the bright-red
color disappeared. Heptane (10 ml) was added to the
pale-yellow solution and it was left for 12 h at r.t. The
residue that precipitated was filtered off and washed
with pentane to give adduct 14, yield 0.14 g (78%),
1
yellow crystals, m.p. 278–279°C. H-NMR: l 3.95 (s,
1H, CH), 4.29 (s, 5H, C5H5), 3.52 (m, 1H), 4.08 (m, 1H),
4.23 (m, 1H), 4.79 (m, 1H) (C5H4), 5.94 (d, 2H, J=1.08
Hz), 7.40–7.60, 7.80–8.00, 8.65–8.78 (m, 11H, arom.).
13C-NMR: l 30.93 (C), 69.08 (C5H5), 67.06, 67.59,
68.51, 69.88 (C5H4), 65.73 (CH), 81.97 (C), 93.52 (Cipso
Fc), 122.22, 125.07, 125.51, 126.75, 127.11, 128.78,
129.38, 129.70, 131.58, 135.37 (CH), 142.71, 161.20,
162.91 (Cipso), 206.10, 208.01 (CꢀO). Anal. Found: C,
70.64; H, 4.57; Fe, 10.82; N, 7.73. C31H23FeN3O2. Calc.
C, 70.87; H, 4.41; Fe, 10.63; N, 8.00%.
Adduct 11, Rf 0.36, yield 0.41 g (65%), yellow needles,
1
m.p. 266–267°C. H-NMR: l 2.55 (d, 1H, CH, J=7.2
Hz), 2.75 (d, 1H, CH, J=7.2 Hz), 3.12 (br.s, 1H), 3.74
(br.s, 1H), 3.96 (br.s, 1H), 4.01 (br.s, 1H) (C5H4), 4.05
(s, 5H, C5H5), 6.45, 6.80, 6.92–7.15, 7.31–7.40, 7.46–
7.65 (m, 21H, arom.). 13C-NMR: l 41.86 (CH), 45.36
(C), 47.82 (CH), 68.77 (C5H5), 63.86, 66.59, 67.25, 69.58
4.8. Reaction of indene 13 with N-phenylmaleimide
A solution of indene 13 (0.12 g, 0.33 mmol) and
N-phenylmaleimide (0.057 g) in benzene (50 ml) was
refluxed for 5 h. The solvent was distilled off in vacuo

184
E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
and the residue was chromatographed (TLC on silica
gel, hexane–benzene, 2:1) to give 0.12 g of the adduct
15, yellow crystals, m.p. 259–260°C. H-NMR: l 3.95
Anal. Found: C, 78.93, H, 4.98, Fe, 15.72. C23H18Fe.
Calc.: C, 78.87; H, 5.18; Fe, 15.95%.
1
(d, 1H, J=9.1 Hz), 4.23 (d, 1H, J=9.1 Hz), 4.25 (s,
5H, C5H5), 4.56 (m, 1H), 4.59 (m, 1H), 4.81 (m, 1H),
4.92 (m, 1H) (C5H4), 4.67 (d, 1H, J=1.25 Hz), 5.352
(d, 1H, J=4.9 Hz), 5.376 (d, 1H, J=4.9 Hz), 7.11–
7.15, 7.29–7.82, 8.40–8.44 (m, 11H, arom.). 13C-
NMR: l 30.35 (C), 39.43, 39.68 (CH), 52.14 (CH),
70.31 (C5H5), 69.71, 69.93, 72.08, 73.13 (C5H4), 73.05
(C), 96.10 (Cipso Fc), 125.32, 125.77, 126.43, 126.53,
126.74, 127.37, 128.33, 128.44, 128.53, 128.82, 129.02,
129.10, 132.39 (CH), 132.58, 134.62, 161.50 (Cipso),
176.43, 179.55 (CꢀO). Anal. Found: C, 75.83; H, 4.65;
Fe, 10.74; N, 2.78. C33H25FeNO2. Calc.: C, 75.72; H,
4.82; Fe, 10.67; N, 2.67%.
4.10. Reaction of cyclopropene 6 with CF3SO3H
Trifluoromethanesulfonic acid (0.5 ml) was added to
a solution of 6 (0.175 g) in CH2Cl2 (20 ml). The
mixture was stirred for 30 min at 20°C under dry
argon and then N,N-dimethylaniline (0.5 ml) was
added. Following conventional work-up and TLC on
silica gel, compounds 17a,b (0.026 g, 11%), Rf 0.42,
and 16 (0.112 g, 64%), Rf 0.36, m.p. 137°C, were
obtained.
4.11. Opening of a small ring in monobromide 7
Aluminum chloride (0.1 g) was added to a solution
of monobromocyclopropane 7 (0.22 g, 0.5 mmol) in
CH2Cl2 (50 ml). The mixture was stirred for 2 h at
20°C under dry argon and then N,N-dimethylaniline
(1 ml) was added. The organic layer was separated
and washed with 1% HCl and water. Following re-
moval of the solvent and TLC on silica gel, indene 16
(0.13 g, 68%), Rf 0.35, m.p. 136–137°C, was obtained.
4.9. Reaction of cyclopropene 6 with HBF4 ·Et2O
A solution of 6 (0.175 g, 0.5 mmol) in dry ether (25
ml) was treated with HBF4 ·Et2O (2 ml). The brown
mixture was stirred in an atmosphere of argon for 1 h
and N,N-dimethylaniline (2 ml) was then added. Stir-
ring continued for an additional 30 min and the mix-
ture was partitioned between benzene (50 ml) and
water (100 ml). The organic layer was separated,
washed several times with 1% HCl and water, and the
solvents were distilled off in vacuo. The residue was
chromatographed (TLC on silica gel, hexane–benzene,
2:1) to give the following products.
The compound propene 12 (0.09 g, 50%) was recov-
ered as a ca. 5:1 mixture of Z-(12a) and E-(12b)
isomers, Rf 0.75, yellow crystals, m.p. 84–86°C. 1H-
NMR for 12b: l 2.17 (d, 3H, CH3, J=7.22 Hz), 4.07
(s, 5H, C5H5), 3.85 (m, 1H), 4.03 (m, 1H), 4.09 (m,
1H), 4.40 (m, 1H) (C5H4), 5.74 (q, 1H, CHꢀ, J=7.22
Hz), 7.34–7.98 (m, 7H, C10H7). Anal. Found: C,
78.59; H, 5.61; Fe, 15.58. C23H20Fe. Calc.: C, 78.43
(compound 6a—78.42%); H, 5.72; Fe, 15.85%.
4.12. Reaction of cyclopropane 9 with
triphenylmethylium tetrafluoroborate
Triphenylmethylium tetrafluoroborate (0.4 g) was
added to a solution of cyclopropane 9 (0.35 g, 1
mmol) in CH2Cl2 (50 ml) at 20°C under dry argon.
The mixture was stirred for 2 h and then worked up
as described above. Following TLC on silica gel (hex-
ane–benzene, 2:1), the following products were iso-
lated: 17a,b (0.025 g, 5%), Rf 0.43; indene 16 (0.081 g,
23%), Rf 0.36, m.p. 136–137°C; and a mixture of two
isomeric butenes 21a and 21b (ca. 2:1), Rf 0.27, yellow
powder, m.p. 186–188°C. Anal. Found: C, 85.11, H,
5.49, Fe, 9.68. C42H34Fe. Calc.: C, 84.84; H, 5.76; Fe,
9.40%. Recrystallization from benzene afforded the in-
dividual isomer 22a, m.p. 213–214°C. 1H-NMR: l
3.56 (d, 2H, J=5.28 Hz), 4.19 (s, 5H, C5H5), 3.89 (m,
1H), 3.98 (m, 1H), 4.26 (m, 1H), 4.81 (m, 1H) (C5H4),
6.93 (t, 1H, J=5.3 Hz), 7.01–8.20 (m, 22H, arom.).
Anal. Found: C, 84.72; H, 5.89; Fe, 9.21. Isomer 22b,
1H-NMR: l 3.50 (d, 2H, J=5.4 Hz), 3.87 (s, 5H,
C5H5), 3.43 (m, 1H), 3.75 (m, 1H), 3.99 (m, 2H)
(C5H4), 6.92 (t, 1H, J=5.4 Hz), 7.10–8.20 (m, 22H,
arom.).
The compound 3-(p-dimethylaminophenyl)-1-ferro-
cenyl-1-(1-naphthyl)prop-1-ene (0.041 g, 17%) was re-
covered as a ca. 1:1 mixture of Z-(17a) and E-(17b)
1
isomers, Rf 0.42, brown oil. H-NMR: l 2.84 (s, 6H,
CH3), 2.89 (s, 6H, CH3), 2.94 (d, 2H, J=6.7 Hz), 2.98
(d, 2H, J=6.62 Hz), 4.06 (s, 5H, C5H5), 4.08 (s, 5H,
C5H5), 4.19 (m, 2H), 4.23 (m, 2H) (C5H4), 4.17 (m,
1H), 4.26 (m, 1H), 4.31 (m, 2H) (C5H4), 6.68 (d, 1H,
J=6.62 Hz), 6.92 (m, 1H, J=6.7 Hz), 7.35–7.60,
7.68–7.75, 7.82–7.90 (m, 11H, arom.). Anal. Found:
C, 79.11, H, 6.29, Fe, 11.64; N, 2.83. C31H29FeN.
Calc.: C, 78.98; H, 6.20; Fe, 11.85%; N, 2.97%.
Indene 16, (0.027 g, 15%), Rf 0.35, yellow crystals,
m.p. 136–137°C. 1H-NMR: l 3.85 (dd, 2H, J=1.2,
6.92 Hz), 4.09 (s, 5H, C5H5), 3.72 (m, 1H), 4.08 (m,
1H), 4.25 (m, 1H), 4.52 (m, 1H) (C5H4), 6.43 (t, 1H,
J=6.95 Hz), 7.15–7.60, 7.75–7.93 (m, 6H, C10H6).
Acknowledgements
We gratefully acknowledge the support of the
CONACyT (Mexico) through Grant 400313-5-3182PE.

E.I. Klimo6a et al. / Journal of Organometallic Chemistry 566 (1998) 175–185
185
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