Cross-conjugated Z- and E-3-ferrocenylmethylidene-4-methyl-2-phenylpenta-1, 4-dienes - Synthesis and some chemical properties

Article abstract of DOI:10.1139/V07-105

Dehydration of (Z)- and (E)-4-ferrocenyl-3-isopropenyl-2-phenylbut-3-en-2- ols and Z-3-ferrocenylmethylidene-4-methyl-2-phenylpentane-2,4-diol affords (Z)- and (E)-3-ferrocenylethylidene-4-methyl-2-phenylpenta-1,4-dienes with a system of three cross-conjugated double bonds. One of the methylidene groups of the trienes obtained is smoothly protonated under the action of tetrafluoroboric acid etherate to yield (Z)- and (E)-3-ferrocenyl-2-isopropenyl1-methyl-1- phenylallyl tetrafluoroborates. The cross-conjugated trienes undergo cationic cycloaddition to these allylic cations as well as proton-induced cyclodimerization resulting in 7-ferrocenyl-4-ferrocenylmethylidene-l,3- dimethyl-5-phenyl-8-(1-phenylethylidene)bicyclo[3.3.1]non-2-ene and isomeric 1,5-diferrocenyl-2,6-diisopropenyl-3,7-diphenylocta1,3,6-trienes.

Full text of DOI:10.1139/V07-105

969
Cross-conjugated Z- and E-3-ferrocenylmethyl-
idene-4-methyl-2-phenylpenta-1,4-dienes —
Synthesis and some chemical properties
Juan Manuel Martínez Mendoza, Lena Ruíz Ramírez, Ruben Alfredo Toscano,
Simon Hernández Ortega, Cecilio Alvarez Toledano, Marcos Flores Alamo, and
Elena I. Klimova
Abstract: Dehydration of (Z)- and (E)-4-ferrocenyl-3-isopropenyl-2-phenylbut-3-en-2-ols and Z-3-ferrocenylmethyl-
idene-4-methyl-2-phenylpentane-2,4-diol affords (Z)- and (E)-3-ferrocenylethylidene-4-methyl-2-phenylpenta-1,4-dienes
with a system of three cross-conjugated double bonds. One of the methylidene groups of the trienes obtained is
smoothly protonated under the action of tetrafluoroboric acid etherate to yield (Z)- and (E)-3-ferrocenyl-2-isopropenyl-
1-methyl-1-phenylallyl tetrafluoroborates. The cross-conjugated trienes undergo cationic cycloaddition to these allylic
cations as well as proton-induced cyclodimerization resulting in 7-ferrocenyl-4-ferrocenylmethylidene-1,3-dimethyl-5-
phenyl-8-(1-phenylethylidene)bicyclo[3.3.1]non-2-ene and isomeric 1,5-diferrocenyl-2,6-diisopropenyl-3,7-diphenylocta-
1,3,6-trienes.
Key words: cross-conjugated trienes, ferrocenylallylic cations, cyclodimerization, cycloaddition, ferrocene.
Résumé : La déshydratation des (Z)- et (E)-4-ferrocényl-3-isopropényl-2-phénylbut-3-én-2-ols et du Z-3-ferrocényl-
méthylidène-4-méthyl-2-phénylpentane-2,4-diol conduit aux (Z)- et (E)-3-ferrocényléthylidène-4-méthyl-2-phénylpenta-
1,4-diènes qui comportent un système à trois doubles liaisons à conjugaison croisée. Sous l’action de l’éthérate de
l’acide tétrafluoroborique, il se produit une protonation facile d’un des groupes méthylènes des triènes qui ont été obte-
nus avec production de tétrafluoroborates de (Z)- et (E)-4-3errocényl-2-isopropényl-1-méthyl-1-phénylallyle. Les triènes
à conjugaison croisée conduisent à une cycloaddition cationique de ces cations allyliques ainsi qu’une cyclodimérisa-
tion induite par les protons qui conduit à la formation du 7-ferrocényl-4-ferrocénylméthylidène-1,3-diméthyl-5-phényl-8-
(1-phényléthylidène)bicyclo[3.3.1]non-2-ène ainsi qu’aux 1,5-diferrocényl-2,6-diisopropényl-3,7-diphénylocta-1,3,6-
triènes isomères.
Mots-clés : triènes à conjugaison croisée, cations ferrocénylallyliques, cyclodimérisation, cycloaddition, ferrocène.
[Traduit par la Rédaction] Mendoza et al. 982
Introduction
chemistry of polymeric materials, biology, and synthetic or-
ganic chemistry (asymmetric synthesis) has appeared since
1994 (3–7).
The ferrocene molecule itself is an energy-rich structure.
Therefore, studies on compounds comprising other energy-
rich fragments, such as ene, diene, and polyene chains, fused
carbo- and hetero-cyclic systems, in addition to the
ferrocene moiety, are of special interest.
Recently, the interest in the chemistry of ferrocenes has
increased because of their possible practical applications.
Data on the industrial use of the ferrocene derivatives, avail-
able from the patent literature (1, 2), reflect mainly their em-
ployment in military-industrial establishment, rocket
technologies, and medicine. Publications demonstrating the
use of ferrocene derivatives in nonlinear optics devices,
Investigations into ferrocene-containing polyene com-
pounds aim at the studies of strain energy, optical properties
of ferrocenylpolyenes, mechanisms of highly selective reac-
tions involved in the in vitro and in vivo syntheses of various
aliphatic, carbocyclic, and heterocyclic compounds, and
their potential use as molecular building blocks and in the
realm of supramolecular chemistry as redox-switching re-
ceptors. The most-studied compounds of this type are repre-
sented by linear ferrocenylalkenes and alka-1,3-dienes (8–
12).
Received 21 February 2007. Accepted 09 July 2007.
Published on the NRC Research Press Web site at
canjchem.nrc.ca on 11 October 2007.
J.M.M. Mendoza, L.R. Ramírez, M.F. Alamo, and
E.I. Klimova.1 Facultad de Química, Universidad Nacional
Autónoma de México, Cd. Universitaria, Coyoacán, C.P.
04510, México D.F., México.
R.A. Toscano, S.H. Ortega, and C.A. Toledano. Instituto de
Química, Universidad Nacional Autónoma de México, Cd.
Universitaria, Coyoacán, C.P. 04510, México D.F., México.
The following approaches are employed for the synthesis
of ferrocenylalka-1,3-dienes and exocyclic ferrocenylalka-
1,2,3-trienes with a terminal methylidene group: dehydration
1Corresponding author: (e-mail: klimova@servidor.unam.mx).
Can. J. Chem. 85: 969–982 (2007)
doi:10.1139/V07-105
© 2007 NRC Canada

970
Can. J. Chem. Vol. 85, 2007
Scheme 1.
CH2
CH2
CH3
BF4
CHFc
CH3
CH3
C
C
C
HBF4
CH3
CH3
C
C
H
H2O
CH3
CH3
C
C
C
H
1) MeLi, 2) H2O
3) H (-H2O)
C
C
C
Fc
Fc
O
CH2
O
1 a,b
3
2
Z - (1a); E - (1b)
Fc = C5H5FeC5H4
Scheme 2.
H3C
CH3
Fc
H3C
CH3 Fc
Fc
H
CH
C
C
DMA
C
CH3
O
C
H
2
3
+
+
C
C
H3C
H
H
C
CH2
CH3
CH3
CH3
CH3
CH3
O
N
DMA =
Fc
CH3
4a
4b
Scheme 3.
CH3
CH3
CH3
H3C
H3C
H3C
CH3
CH2
H3C
CH2
F
e
Fc
H
CH3
CH3
C
C
H
H
H3C
Fc
CH3
H3C
CH3
CH3
C
C
H3C
Fc
+
+
CH2
H
H
H
Fc
Fc
Fc
7
2
5
6
of ferrocenyl(methyl)allylic alcohols (13–15), deprotonation
of ferrocenyl(methyl)allyl cations (13–18), and the Wittig
reaction (19). Diferrocenyl-, aryl- and alkylferrocenyl-, aryl-,
and alkyldiferrocenylbuta-1,3-dienes and 1,3-bis(ferrocenyl-
methylidene)-2-methylidenecycloalkanes have been synthe-
sized (20, 21), and their highly diastereoselective thermally
induced and acid-catalyzed cyclodimerization (13–22) and
cationic cycloaddition (15, 19–22) have been studied. The
reaction products comprised ferrocenyl-substituted six-
membered carbocycles or carbocycles fused to other carbo-
or hetero-cyclic systems. Some of them possessed high bio-
logical activities (17). Experimental evidence of the stepwise
non-synchronous mechanism of acid-catalyzed cyclodimeri-
zation has been obtained (22), which is of theoretical signifi-
cance.
With relation to synthetic and theoretical organic chemis-
try and the chemistry of high-molecular-mass compounds, it
was of interest to inquire into the question of a feasibility of
synthesizing the simplest representatives of linear cross-
conjugated ferrocenyl-substituted trienes and to study their
properties.
Scheme 4.
CH2
CH2
CH3
Ph
C
C
C
Fc
H
CH3
Ph
C
C
C
H
C
C
Fc
CH2
CH2
E- 8b
Z- 8a
of the type (4–7) (Schemes 1–3). Naturally, it was suggested
that the formation of the cyclodimers 4–7 is a characteristic
feature of cross-conjugated heterotrienes of the type 1a, 1b,
and triene 2.
In continuation of our previous studies, we synthesized
isomeric (Z)- and (E)-3-ferrocenylmethylidene-4-methyl-2-
phenylpenta-1,4-dienes (8a, 8b) (Scheme 4) as the new rep-
resentatives of the cross-conjugated linear trienes and stud-
ied some of their chemical properties.
Previously, we have reported the synthesis of isomeric
(Z)- and (E)-2-acetyl-1-ferrocenyl-3-methylbuta-1,3-dienes
(1a, 1b) (23) and 3-ferrocenylmethylidene-2,4-dimethylpenta-
1,4-diene (2) (24), a new type of cationic cycloaddition of
the triene 2 to a cation (3) and acid-catalyzed cyclo-
dimerization of the triene 2 resulting in polycyclic structures
Results and discussion
(Z)- and (E)-2-Acetyl-1-ferrocenyl-3-methylbuta-1,3-dienes
(1a and 1b) and ethyl 2-benzoyl-ferrocenylacrylate (9)
(Schemes 5 and 6) served as the starting compounds for the
synthesis of the target trienes (8a) and (8b).
© 2007 NRC Canada

Mendoza et al.
971
Scheme 5.
O
C
CH2
C
CH2
C
1) MeLi / THF
2) AcOH
CH3
CH3
CH3
CH3
H
CH3
CH3
Fc
H
C CHFc
C C
C C
+
C
O
C
O
Fc
C
O
E- 1b
Z- 1a
Scheme 6.
O
CHO
EtO
Ph
C
H
O
C
C
Fe
Ph
C CH2 COOEt
+
C
O
Fc
E- 9
Compound 9 was obtained in high yield as a single iso-
mer. The spatial structure of compound 9 was established on
the basis of the X-ray diffraction analysis of a single crystal
of compound 9 prepared by crystallization from dichloro-
methane (Table 1). The general view of the molecule 9 is
shown in Fig. 1, and no special comments are needed. The
X-ray results indicate that compound 9 has an (E)-configura-
tion. (Z)-2-Acetyl-1-ferrocenyl-3-methylbuta-1,3-diene (1a)
was found to react with PhLi to yield a mixture of 1,2- (10a)
and 1,4-addition products (11a and 11b) in a ~1:1 ratio,
whereas the (E)-isomeric diene 1b affords the (E)-isomeric
alcohol (10b) (Scheme 7).
Fig. 1. Molecular structure of 9.
Compounds 10a and 11 were separated by column chro-
1
matography on alumina. According to the data from H and
13C NMR spectra, the ferrocenyl ketone 11 is formed as a
~2:1 mixture of two diastereomers. They were separated by
TLC on SiO2; the structure of the major diastereomer 11a
was established by X-ray diffraction analysis on the single
crystal grown by crystallization from chloroform. The gen-
eral view of the molecule 11a is shown in Fig 2, and its
principal geometric parameters are presented in Table 1
without special comments. The results obtained suggest that
11a is (S,S)-4-ferrocenyl-3-isopropenyl-4-phenylbutan-2-one
(eclipsed conformation), and compound 11b has apparently
(S,R)-configuration.
The structures of compounds 10a and 10b were addition-
ally confirmed by the data from H and 13C NMR and by
1
formation of a Diels–Alder adduct (12) with N-phenylazo-
The general view of compound 13 is shown in Fig. 3, and its
geometric parameters (25) are given in Table 1.
Our attempts to establish configurations of the diastereo-
meric hydroxy ketones 14a and 14b failed.
We have found that all alcohols obtained (10a, 10b, 13,
14a, and 14b) underwent smooth dehydration when treated
with POCl3 in pyridine at 20 °C. The alcohols 10a, 10b, and
13 afforded mixtures of isomeric (Z)- and (E)-3-ferrocenyl-
ethylidene-4-methyl-2-phenylpenta-1,4-dienes (8a and 8b)
(Scheme 10).
1
dicarboximide (Scheme 8). According to the H NMR spec-
tra of compound 12, it was formed as a single diastereomer,
which suggests the stereospecificity of the process. Ethyl 2-
benzoyl-3-ferrocenylacrylate (9) reacts with MeLi like
acetylbutadiene (1a) to give a diol (13) and a hydroxy
ketone (14) in a ~2:1 ratio (1H NMR data) (Scheme 9); the
latter being a ~5:1 mixture of two diastereomers, 14a and
14b.
These compounds were separated by column chromatog-
raphy on Al2O3 and characterized by the data from mass
spectrometry, elemental analysis, and 1H and 13C NMR
spectroscopy. The structure of the diol 13, including its (Z)-
configuration, was established by X-ray diffraction analysis
of a single crystal grown by crystallization from chloroform.
Dehydration of the hydroxy ketones 14a (or 14b) did not
affect the chiral centers to yield compounds 15a (or 15b),
respectively, as single diastereomeric forms (Scheme 11).
The structures of these enones were confirmed by the data
1
from mass spectrometry, elemental analysis, and H and 13C
© 2007 NRC Canada

972
Can. J. Chem. Vol. 85, 2007
Table 1. Selected bond lengths and bond angles for compounds 6, 9, 11a, and 13.
Selected bond lengths
r (Å)
Selected bond angles
ω (°)
6
C(1)—C(9)
C(5)—C(9)
C(4)—C(12)
C(1)—C(8)
C(7)—C(8)
C(5)—C(6)
C(5)—C(4)
C(3)—C(4)
C(1)—C(2)
1.534(6)
1.520(6)
1.341(6)
1.552(6)
1.534(6)
1.566(6)
1.539(6)
1.485(6)
1.505(6)
C(1)–C(9)–C(5)
C(8)–C(1)–C(9)
C(9)–C(1)–C(2)
C(9)–C(5)–C(4)
C(1)–C(8)–C(7)
C(1)–C(2)–C(3)
C(35)–C(34)–C(36)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
112.7(4)
109.1(4)
105.4(4)
107.9(4)
115.3(4)
125.0(4)
111.4(4)
116.1(4)
109.4(4)
9
C(1)—C(11)
C(11)—C(12)
C(12)—C(13)
C(13)—O(1)
C(12)—C(20)
C(20)—O(2)
C(20)—O(3)
1.459(3)
1.341(3)
1.509(3)
1.214(3)
1.483(3)
1.201(3)
1.341(3)
C(1)–C(11)–C(12)
C(11)–C(12)–C(20)
C(11)–C(12)–C(13)
C(20)–C(12)–C(13)
C(1)–C(11)–H(11)
C(12)–C(13)–O(1)
C(12)–C(20)–O(2)
129.0(2)
118.0(2)
124.3(2)
117.71(19)
115.5
119.2(2)
125.4(2)
11a
C(1)—C(11)
C(11)—C(12)
C(11)—C(20)
C(19)—O(1)
C(19)—C(20)
C(20)—C(21)
C(21)—C(23)
1.513(3)
1.517(3)
1.557(3)
1.204(2)
1.513(3)
1.512(3)
1.389(3)
C(1)–C(11)–C(12)
C(12)–C(11)–C(20)
C(11)–C(20)–C(19)
C(19)–C(20)–C(21)
C(23)–C(21)–C(22)
C(23)–C(21)–C(20)
C(20)–C(19)–O(1)
112.65(17)
109.18(16)
109.76(17)
109.08(17)
121.6(2)
117.9(2)
121.8(2)
13
C(1)—C(2)
C(2)—C(3)
C(3)—C(4)
C(2)—O(1)
C(3)—C(7)
C(4)—O(2)
C(7)—C(8)
1.526(4)
1.538(4)
1.539(4)
1.447(3)
1.341(3)
1.453(3)
1.463(4)
C(1)–C(2)–O(1)
C(1)–C(2)–C(3)
C(4)–C(3)–C(7)
C(2)–C(3)–C(7)
C(18)–C(4)–C(3)
C(5)–C(4)–O(2)
C(18)–C(4)–O(2)
103.7(2)
114.4(2)
122.3(3)
119.1(3)
111.5(2)
106.2(2)
106.6(2)
Scheme 7.
CH2
CH2
CH2
C
Ph
1) PhLi
CH3
C
C
H
CH3
CH3
C
H
CH3
CH3
C
C
C
C
CH CH Fc
+
Ph
CH3
Fc
C
O
Fc
C
2) H2O
OH
O
1a
11a and 11b
Z- 10a
CH2
CH2
1) PhLi
2) H2O
CH3
CH3
C
C
C
Fc
H
CH3
C
C
Fc
H
C
C
C
Ph
CH3
OH
O
1b
E- 10b
NMR spectroscopy (see Experimental Section); however, we
could not establish their configurations.
isomer, viz., (E)-3-ferrocenylethylidene-4-methyl-2-phenylpenta-
1,4-diene 8b (Scheme 12).
Dehydration of the alcohols 10a, 10b, and 13 under the
action of boiling acetic acid afforded only one geometrical
In our opinion, the change in the initial (Z)- or (E)-config-
uration of the tertiary alcohols (see Schemes 8 and 10) in the
© 2007 NRC Canada

Mendoza et al.
973
Fig. 2. Molecular structure of 11a.
Fig. 3. Molecular structure of 13.
Scheme 8.
O
O
C
N
CH3
Ph
CH3
N
Ph
C
N
N
N
C
O
N
Ph
10a
C
O
OH
Fc
10b
12
Scheme 9.
OH
CH3
OH
O
CH3
CH3
C
EtO C
H
1) MeLi
2) H2O
CH3
CH3
C
C
H
C C
CH CH Fc
C C
OH
+
Ph
C
O
Fc
Ph
C
Ph
CH3
Fc
O
9
14a and 14b
13
dehydration into (E)- and (Z)-trienes, respectively, results
upon the rotation about the sesquialteral C(1)–C(2) bonds in the
transient tetrafluoroborates of the ferrocenyl(methyl)phenyl-
allylic cations (16a) and (16b) despite the fairly high ener-
getic barrier (26–29) (Scheme 13).
This suggestion has been confirmed in the studies of the
chemical behavior of tetrafluoroborates of the allylic cations
16a and 16b obtained upon action of tetrafluoroboric acid
etherate on the trienes 8a and 8b (Scheme 14).
16a and 16b contain multiplets for the protons of the methyl
groups of the CH3–C=CH2 fragments with a characteristic
allylic coupling constant and the corresponding multiplets
for the protons of the =CH2 groups alongside low-field
singlets for the protons of the methyl groups of the Ph–C–
CH3 fragments, which supports their structures.
In solutions (CD2Cl2), the salts 16a and 16b undergo
gradual isomerization to form mixtures of two isomers
(16a ꢀ 16b and 16b ꢀ 16a) in variable proportions de-
1
Treatment of the trienes 8a and 8b with HBF4 – Et2O re-
sults in crystalline salts 16a and 16b because of the
protonation of only one CH2=C group, namely, that bearing
the phenyl substituent, and the formation of the most-stable
pending on the time of the experiment, judging from the H
NMR data.
Deprotonation of the solid tetrafluoroborates 16a and 16b
under the action of N,N-dimethylaniline resulted in virtually
pure original trienes 8a and 8b, respectively. Treatment of
1
phenylallylic cations. The H NMR spectra of the cations
© 2007 NRC Canada

974
Can. J. Chem. Vol. 85, 2007
Scheme 10.
CH2
CH2
CH2
POCl3 ,
CH3
Ph
C
C
C
H
CH3
Ph
C
C
C
Fc
C
CH3
C
C
C
H
N
C
+
C
Fc
H
20°C
Ph
CH3
Fc
CH2
CH2
OH
10a
E- 8b
Z- 8a
(60%)
(18%)
(20%)
(65%)
CH2
POCl3 ,
20°C
CH3
C
C
C
Fc
H
N
C
8b
8a
+
Ph
CH3
OH
10b
CH3
CH3
OH
POCl3 ,
20°C
C
H
N
8b
8a
(28%)
C
C
(58%)
+
Ph
CH3
C
Fc
OH
13
Scheme 11.
Scheme 12.
CH2
C
CH2
CH3
POCl3, PyH
20 °C
CH3
Ph
CH3
Ph
C
14 a (14 b)
CH CH Fc
Fc
H
AcOH, T°
C
O
CH C
10a, 10b, 13
C
–H2O
15 a (15 b)
CH2
8b
solutions of the salts 16a and 16b in CH2Cl2 with N,N-
dimethylaniline at 20 °C for prolonged periods (1–2 h) af-
forded mixtures of the isomeric trienes 8a and 8b with (E)-
isomer 8b predominating.
The trienes 8a and 8b are orange powders; they undergo
oxidation and polymerization upon storage under ordinary
conditions. In boiling benzene, they form [4+2]-cyclo-
adducts with N-phenylmaleimide (Scheme 15).
isopropenyl groups with characteristic multiplicities of the
–CH3 and =CH2 groups.
Boiling of the trienes 8a and 8b in a 10:1 mixture of ace-
tic and trifluoroacetic acids afforded dimerization products
with linear (18a–18c) and cyclic (19) structures (Scheme 16).
The linear dimer 18 was obtained as a ~3:2:1 mixture of
three isomers (1H NMR data), which were separated by TLC
The adduct (17) was isolated as a ~3:1 mixture of exo-17a
and endo-17b isomers (1H NMR data), which were sepa-
rated by TLC on silica gel. Their structures were confirmed
1
on SiO2 and characterized by mass and H and 13C NMR
spectra and data from elemental analysis, but their spatial
structures have yet to be elucidated.
1
by the data from H and 13C NMR spectra, and assignment
to the exo- and endo-isomers was made based on the previ-
ously established criteria (13, 14, 23). Assigining the adduct
17a to the exo-series resulted from the fact that the signals
for all the protons of the C5H4 moiety of the ferrocene unit
The cyclodimer 19 was isolated as a single diastereomer
(yield: ~20%). The H NMR spectrum of this compound
1
contained three singlets for the methyl groups, two singlets
for the olefinic protons, signals for the protons of two
ferrocenyl and two phenyl fragments, a doublet of doublets
and a singlet for the protons of two mtethylene groups, and a
doublet of doublets of a methine proton. The 13C NMR spec-
trum contained signals for the carbon atoms of two ferrocene
units, three methyl, two methylene, and one methine groups,
eight carbon atoms bearing no protons, and two olefinic car-
bon atoms. The spectroscopic data confirm unequivocally
1
appeared in a lower field of the H NMR spectrum than
those of the unsubstituted cyclopentadienyl ring. For the iso-
mer 17b, the multiplet for two protons of the C5H4 moiety
(δ = 4.10) occurred in a higher field than the singlet for the
protons of the C5H5 group (δ 4.18), which is typical of endo-
adducts of ferrocenyl-substituted 1,3-dienes. The spectra of
the adducts 17a and 17b contained signals for the
© 2007 NRC Canada

Mendoza et al.
975
Scheme 13.
CH2
CH2
CH3
Fc
CH3
H
H
H
CH3
10b
CH3
Ph
10a, 13
Ph
H
Fc
AcO
AcO
16b
16a
20°C
8a + 8b
100°C
8b
Scheme 14.
CH2
CH2
CH3
BF4
HBF4· Et2O
CH3
Ph
C
C
C
H
CH2Cl2
20°C
H
C
CH3
Ph
16a + 16b
Fc
Fc
CH2
16a
8a
CH2
CH2
CH3
BF4
HBF4· Et2O
CH3
Ph
C
C
C
Fc
CH2Cl2
20°C
Fc
C
CH3
Ph
16b + 16a
H
H
CH2
16b
8b
Scheme 15.
O
C
O
C
O
C
HC
HC
N
Ph
Ph
Ph
C
O
8a
8b
N
Ph
N
Ph
CH3
CH3
+
C
C
O
O
CH2 Fc
CH2 Fc
17b
17a
the cyclic structure of compound 19 analogous to that of
compound 6.
The structure of the cyclodimer 6 has been elucidated re-
cently. According to the data from X-ray analysis of a single
crystal prepared by crystallization from ethanol, the
The main geometric parameters of this compound are
listed in Table 1. The values of the C–C and C=C bond
lengths in the carbocyclic fragments as well as of the Fe–C
and C–C bond lengths and the geometric parameters of the
ferrocene sandwiches are similar to the standard ones.
The compounds 18a–18c and 19 were obtained from the
reactions of the trienes 8a and 8b with the tetrafluoroborates
16a and 16b (Scheme 17).
cyclodimer
6 is 7-ferrocenyl-4-ferrocenylmethylidene-8-
isopropylidene-1,3,5-trimethylbicyclo[3.3.1]non-2-ene with
a system of two fused six-membered rings (Fig. 4).
© 2007 NRC Canada

976
Can. J. Chem. Vol. 85, 2007
Scheme 16.
CH3
Ph
C
H
C
Fc
Ph
CH3
CH
8a
Ph
C
Fc
Fc
C
AcOH, CF3COOH
C
C
C
CH2
H
+
CH3
CH3
C
H
CH3
CH2
8b
CH3
Ph
H
Fc
18a–18c
19
Fig. 4. Molecular structure of 6.
tailed investigations aimed at revealing hitherto unknown
processes of intermolecular interactions.
Experimental
1
The H and 13C NMR spectra were recorded on a Unity
Inova Varian spectrometer (300 and 75 MHz, respectively)
for solutions in CDCl3 with Me4Si as the internal standard.
The mass spectra were obtained on a Varian MAT CH-6 in-
1
strument (EI MS, 70 eV). The H NMR spectra of the tetra-
fluoroborates 16a and 16b were recorded for solution in
CD2Cl2. An Elemental Analysis system (GmbH) was used
for elemental analyses. IR spectra were obtained for KBr
pellets on a PerkinElmer FTIR Spectrophotometer model
1605. Chromatographic separations were carried out on col-
umns with alumina (Brockmann activity III).
The following reagents were purchased from Aldrich:
ferrocenecarbaldehyde, 99%; pentane-2,4-dione, 99%; ethyl
benzoylacetate, tech., 90%; methyllithium, 1.6 mol/L solu-
tion in diethyl ether; phenyllithium, 1.9 mol/L solution in
cyclohexane–ether; acetic acid, glacial, 99.99%; N,N-
dimethylaniline, 99%; N-phenylmaleimide, 97%; 4-phenyl-
1,2,4-triazoline-3,5-dione, 98%; and pyridine, 99%.
Tetrafluoroboric acid etherate, 50%–52%, was purchased
from Alfa Aesar.
Scheme 17.
1) 16a ; 16b
18a–18c
19
+
8a
8b
(Z)- and (E)-2-Acetyl-1-ferrocenyl-3-methyl-1,3-
butadienes (1a) and (1b)
These compounds were prepared by reaction of 3-
+
2) DMA
~ 40%
~30%
(ferrocenylmethylidene)pentane-2,4-dione
methyllithium in tetrahydrofuran.
(23)
with
The formation of compounds 18 and 19 seems to result
from intramolecular transformation of an intermediate
dimeric linear allylic cations (20) and (21) according to
Scheme 18.
Deprotonation of the linear cation 20 under the action of
N,N-dimethylaniline results in linear dimers 18a–18c, while
deprotonation of a bicyclic carbocation existing in equilib-
rium with the former cation yields the product 19.
The stereospecific character of the formation of the
cyclodimer 19 can apparently be rationalized by configura-
tional features of the intermediate dimeric allylic cation 20
where the carbenium center and the carbon atom of the
=CH2 group, on one hand, and the terminal methylidene
fragment and the carbon atom of the isopropenyl group, on
the other hand, are spatially proximal to enable
intramolecular double alkylation. In our opinion, studies of
the effects of diverse factors on the features of dimerization
of linear cross-conjugated trienes deserve undoubtedly de-
(Z)-2-Acetyl-1-ferrocenyl-3-methyl-1,3-butadiene (1a)
Yield: 70%; orange crystals, mp 58–60 °C (mp 58 –60 °C
(23)). MS m/z: 294 [M].
(E)-2-Acetyl-1-ferrocenyl-3-methylbuta-1,3-diene (1b)
Yield: 76%; red crystals, mp 84–85 °C (mp 84–85 °C
(23)). MS m/z: 294 [M].
Cyclomerization of 3-ferrocenylmethylidene-2,4-
dimethylpenta-1,4-diene (2)
Compound 6 was obtained by dimerization of 3-
ferrocenylmethylidene-2,4-dimethylpenta-1,4-diene (2) ac-
cording to the known procedure (23, 24). The reaction prod-
ucts were separated by preparative TLC on silica gel
1
(hexane). The physical and H NMR spectroscopic charac-
© 2007 NRC Canada

Mendoza et al.
977
Scheme 18.
Ph
Fc
Ph
C
Fc
H3C
CH3
CHFc
CH
Ph
CH2
CH2
DMA
C
8a, 8b
16a,16b
C
C
+
Ph
C
CH2
CH3
C
CH3
CHFc
CH3
CH3
20
20
H
Ph
CH3
Fc
18a–18c
CH3
H
19
Ph
CHFc
H
CH3
21
teristics of compound 6 were in accord with the literature
data (24).
ter (2 × 20 mL), and dried (Na2SO4). The solvent was re-
moved in vacuo, and the residue was chromatographed on
Al2O3 (hexane–ether, 2:1) to give 0.74 g (40%) of the alco-
hol 10a ((Z)-isomer) and 0.72 g (39%) of the ketone 11a and
11b (~2:1). The compounds 11a and 11b were separated by
preparative TLC on silica gel (hexane).
7-Ferrocenyl-4-ferrocenylmethylidene-8-isopropylidene-
1,3,5-trimethylbicyclo[3.3.1]non-2-ene (6)
Yield: 10%; orange crystals, mp 204–205 °C (mp 204–
205 °C (24)). MS m/z: 584 [M]+.
(Z)-4-Ferrocenyl-3-isopropenyl-2-phenyl-3-buten-2-ol (10a)
Yield: 40%; yellow crystals, mp 142–143 °C. IR
(KBr, cm–1): 820, 851, 1002, 1100, 1467, 1643, 1667, 1845,
(E)-Ethyl 2-(ferrocenylmethylidene)benzoylacetate (9)
A
mixture of FcCHO (4.3 g, 0.02 mol), ethyl
1
3030, 3340. H NMR (300 MHz, CDCl3) δ: 1.67 (3H, dd,
benzoylacetate (3 mL), piperidine (1 mL), and pyridine
(1 mL) in dry benzene (100 mL) was refluxed for 10 h. The
reaction mixture was washed with 5% HCl to remove the
amines, and the organic layer was concentrated to dryness.
Diethyl ether (100 mL) was added to the residue, and the
precipitate was filtered off and dried on a filter to give (E)-
ethyl 2-(ferrocenylmethylidene)benzoylacetate 9: yield
6.01 g (81%), dark red crystals, mp 157–158 °C. IR
(KBr, cm–1): 818, 845, 1102, 1478, 1663, 1690, 1850, 1716,
J = 1.2 and 1.5 Hz, CH3), 1.84 (3H, s, CH3), 2.50 (1H, bs,
OH), 4.06 (5H, s, C5H5), 4.10 (2H, m, C5H4), 4.21 (2H, m,
C5H4), 4.54 (1H, dd, J = 1.2 and 2.4 Hz, CH2=), 4.92 (1H,
dd, J = 1.5, 2.4 Hz, CH2=), 6.28 (1H, s, CH=), 7.28–7.45
(5H, m, C6H5). MS m/z: 372 [M]+. Anal. calcd. for
C23H24FeO: C 74.20, H 6.50, Fe 15.00; found: C 74.38, H
6.66, Fe 14.79.
1
4-Ferrocenyl-3-isopropenyl-4-phenyl-2-butanon (11a)
Yield: 20%; orange crystals, mp 178–179 °C. IR
(KBr, cm–1): 821, 834, 1025, 1103, 1473, 1640, 1658, 1708,
3030. H NMR (30 MHz, CDCl3) δ: 1.14 (3H, t, J = 7.2 Hz,
CH3), 4.14 (5H, s, C5H5), 4.18 (2H, q, J = 7.2 Hz, CH2),
4.27 (2H, m, C5H4), 4.31 (2H, m, C5H4), 7.45–7.62 (3H, m,
C6H5), 7.78 (1H, s, CH=), 7.96 (2H, m, C6H5). 13C NMR
(75 MHz, CDCl3) δ: 14.02 (CH3), 61.01 (CH2), 70.92, 71.75
(C5H4), 69.75 (C5H5), 76.69 (CipsoFc), 128.69, 129.10,
133.66 (C6H5), 143.94 (CH=), 126.42, 136.55 (2C), 165.16,
195.90 (2 C=O). MS m/z: 388 [M]+. Anal. calcd. for
C22H20FeO3: C 68.08, H 5.18, Fe 14.39; found: C 68.18, H
5.21, Fe 14.27.
1
1912, 3030. H NMR (300 MHz, CDCl3) δ: 1.60 (3H, dd,
J = 0.9 and 1.5 Hz, CH3), 1.88 (3H, s, CH3), 3.72 (1H, d, J =
11.7 Hz, CH), 3.76 (5H, s, C5H5), 3.97 (1H, m, C5H4), 4.02
(1H, d, J = 11.7 Hz, CH), 4.04 (1H, m, C5H4), 4.07 (2H, m,
C5H4), 4.88 (1H, bs, CH2=), 4.90 (1H, dd, J = 0.9 and
1.8 Hz, CH2=), 7.20 (1H, m, C6H5), 7.32–7.40 (4H, m,
C6H5).
MS m/z: 372 [M]+. Anal. calcd. for C23H24FeO: C
74.20, H 6.50, Fe 15.00; found: C 74.09, H 6.59, Fe 15.11.
The reactions of the dienes (1a) and (1b) with
phenyllithium
4-Ferrocenyl-3-isopropenyl-4-phenyl-2-butanon (11b)
Yield: 12%; orange crystals, mp 184–186 °C. IR
(KBr, cm–1): 820, 832, 1009, 1102, 1469, 1648, 1662, 1716,
A solution of PhLi (1.9 mol/L solution in cyclohexane –
diethyl ether, 15 mL) was added to a stirred solution of com-
pound 1a (1.47 g, 5 mmol) in dry benzene (100 mL); the
mixture was stirred for additional 30 min at 20 °C, and the
excess of phenyllithium was quenched by addition of water
(50 mL). The organic layer was separated, washed with wa-
1
1926, 3024. H NMR (300 MHZ, CDCl3) δ: 1.67 (3H, dd,
J = 1.2 and 1.5 Hz, CH3), 1.96 (3H, s, CH3), 3.83 (1H, d, J =
11.1 Hz, CH), 3.98 (5H, s, C5H5), 4.03 (2H, m, C5H4), 4.09
(1H, d, J = 11.1 Hz, CH), 4.13 (2H, m, C5H4), 4.67 (1H, bs,
© 2007 NRC Canada

978
Can. J. Chem. Vol. 85, 2007
CH2=), 4.75 (1H, dd, J = 1.2 and 2.1 Hz, CH2=), 7.28–7.54
(5H, m, C6H5). MS m/z: 372 [M]+. Anal. calcd. for
C23H24FeO: C 74.20, H 6.50, Fe 15.00; found: C 74.31, H
6.35, Fe 15.18.
(Z)-4-Ferrocenylmethylidene-4-methyl-2-phenylpentan-2,4-
diol (13)
Yield: 50%; yellow crystals, mp 142–143 °C. IR
(KBr, cm–1): 764, 858, 1006, 1101, 1460, 1642, 1670, 1859,
3030, 3343–3408. 1H NMR (300 MHz, CDCl3) δ: 1.65
(3H, s, CH3), 1.67 (3H, s, CH3), 1.73 (3H, s, CH3), 3.42
(1H, bs, OH), 4.04 (5H, s, C5H5), 3.45 (1H, m, C5H4), 3.88
(1H, m, C5H4), 4.06 (1H, m, C5H4), 4.10 (1H, m, C5H4),
4.13 (1H, bs, OH), 6.45 (1H, s, CH=), 7.27–7.55 (5H, m,
C6H5). 13C NMR (75 MHz, CDCl3) δ: 29.67, 31.85, 32.63 (3
CH3), 67.90, 67.99, 69.25, 70.94 (C5H4), 68.97 (C5H5),
76.78, 79.21 (2 C–OH), 82.86 (CipsoFc), 123.02 (CH=),
126.13, 127.28, 128.37 (C6H5), 148.40, 148.67 (2 C).
MS m/z: 390 [M]+. Anal. calcd. for C23H24FeO: C 70.77, H
6.72, Fe 14.32; found: C 70.59, H 6.86, Fe 14.47.
(E)-4-Ferrocenyl-3-isopropenyl-2-phenyl-3-buten-2-ol (10b)
Analogously, the reaction of the diene 1b (1.47 g,
5 mmol) with PhLi gave 1.34 g of the alcohol (E)-10b.
Yield: 72%; orange powder, mp 174–175 °C. IR (KBr, cm–1):
818, 850, 1012, 1109, 1446, 1648, 1671, 1845, 3032, 3345.
1H NMR (300 MHz, CDCl3) δ: 1.60 (3H, dd, J = 0.9 and
1.2 Hz, CH3), 1.75 (3H, s, CH3), 2.44 (1H, bs, OH), 4.10
(5H, s, C5H5), 4.18 (2H, m, C5H4), 4.45 (2H, m, C5H4), 4.65
(1H, dd, J = 0.9, 2.1 Hz, CH2=), 5.09 (1H, dd, J = 1.2 and
2.1 Hz, CH2=), 6.31 (1H, s, CH=), 7.32–7.61 (5H, m, C6H5).
MS m/z: 372 [M]+. Anal. calcd for C23H24FeO: C 74.20, H
6.50, Fe 15.00; found: C 74.17, H 6.37, Fe 15.19.
3-Benzoyl-4-ferrocenyl-2-methyl-2-pentanol (14a)
Yield: 17%; orange crystals, mp 121–122 °C. IR
(KBr, cm–1): 764, 849, 1005, 1103, 1468, 1649, 1668, 1710,
1929, 3034, 3358. 1H NMR (300 MHz, CDCl3) δ: 1.20
(3H, s, CH3), 1.36 (3H, s, CH3), 1.42 (3H, d, J = 7.2 Hz,
CH3), 3.30 (1H, m, J = 3.9 and 7.2 Hz, CH), 3.52 (1H, d, J
= 3.9 Hz, CH), 3.91 (1H, br s, OH), 4.09 (5H, s, C5H5), 3.66
(1H, m, C5H4), 3.82 (1H, m, C5H4), 4.05 (1H, m, C5H4),
4.17 (1H, m, C5H4), 7.23–7.60 (5H, m, C6H5). 13C NMR
(75 MHz, CDCl3) δ: 16.97, 28.07, 30.19 (3 CH3), 33.29,
60.80 (2 CH), 66.97, 67.21, 67.65, 67.81 (C5H4), 68.84
(C5H5), 72.95 (C–OH), 95.31 (CipsoFc), 128.09, 128.60,
132.99 (C6H5), 138.56 (Cipso), 206.43 (C=O). MS m/z: 390
[M]+. Anal. calcd. for C23H24FeO: C 70.77, H 6.72, Fe
14.32; found: C 70.63, H 6.81, Fe 14.41.
Condensation of the hydroxydienes (10a) and (10b)
with 4-phenyl-1,2,4-triazoline-3,5-dione
4-Phenyl-1,2,4-triazoline-3,5-dione (0.2 g, 1.22 mmol)
was added portionwise to a stirred solution of the diene 10a
(or 10b) (0.37 g, 1 mmol) in benzene (30 mL) at 0–5 °C as
the solution discolored. Stirring was continued for an addi-
tional 1 h, and the solvent was evaporated. Column chroma-
tography of the residue on Al2O3 (hexane–dichloromethane,
2:1) gave the adduct 12.
N-Phenyl-3-ferrocenyl-5-methyl-4-(1-phenyl-1-hydroxy-
ethyl)-1,2,3,6-tetrahydropyridazine-1,2-dicarboximide (12)
Yield: 0.40 g (from 10a) (73%), 0.44 g (from 10b); yel-
3-Benzoyl-4-ferrocenyl-2-methyl-2-pentanol (14b)
1
low crystals, mp 223–225 °C. H NMR (300 MHz, CDCl3)
Yield: 6%; orange crystals, mp 136–137 °C. IR (KBr, cm–1):
763, 853, 1004, 1107, 1478, 1656, 1668, 1715, 1932, 3033,
δ: 1.26 (3H, bs, CH3), 1.67 (3H, s, CH3), 2.19 (1H, s, OH),
4.01 (1H, d, J = 16.5 Hz, CH2), 4.16 (1H, d, J = 16.5 Hz,
CH2), 4.25 (5H, s, C5H5), 4.21 (2H, m, C5H4), 4.27 (1H, m,
C5H4), 4.44 (1H, m, C5H4), 6.28 (1H, s, CH), 7.28–7.63
(10H, m, 2 C6H5). 13C NMR (75 MHz, CDCl3) δ: 18.09,
27.21 (2 CH3), 48.41 (CH2), 50.56 (CH), 65.88, 67.09,
68.15, 69.96 (C5H4), 69.12 (C5H5), 90.72 (CipsoFc), 125.50,
125.78, 127.79, 128.07, 128.67, 129.23 (2 C6H5), 75.20,
122.58, 131.60, 139.90, 146.91 (5 C), 148.78, 152.91 (2
C=O). MS m/z: 548 [M]+. Anal. calcd. for C31H29FeN3O3: C
68.02, H 5.34, Fe 10.20, N 7.67; found: C 67.87, H 5.38, Fe
10.32, N 7.71.
1
3367. H NMR (300 MHz, CDCl3) δ: 1.23 (3H, s, CH3),
1.30 (3H, s, CH3), 1.40 (3H, d, J = 6.9 Hz, CH3), 3.28
(1H, m, CH), 3.46 (1H, d, J = 5.4 Hz, CH), 3.90 (1H, br s,
OH), 4.04 (5H, s, C5H5), 3.70 (1H, m, C5H4), 3.79 (1H, m,
C5H4), 3.87 (1H, m, C5H4), 3.96 (1H, m, C5H4), 7.30–7.64
(5H, m, C6H5). 13C NMR (75 MHz, CDCl3) δ: 18.02, 29.01,
30.05 (3 CH3), 34.52, 60.05 (2 CH), 67.40, 67.51, 67.90,
68.65 (C5H4), 68.75 (C5H5), 72.30 (C–OH), 95.30 (CipsoFc),
128.25, 128.47, 128.55 (C6H5), 133.25 (Cipso), 204.05
(C=O). MS m/z: 390 [M]+. Anal. calcd. for C23H24FeO: C
70.77, H 6.72, Fe 14.32; found: C 70.85, H 6.61, Fe 14.52.
The reactions of the E-ethyl 2-(ferrocenylmethyl-
idene)benzoylacetate (9) with methyllithium
Dehydration of the alcohols (10a), (10b), (13), (14a),
and (14b) with POCl3–PyH
A solution of MeLi (1.6 mol/L solution in diethyl ether,
20 mL) was added to a stirred solution of compound 9
(1.94 g, 5 mmol) in dry benzene (100 mL); the mixture was
stirred for additional 30 min at 20 °C, and the excess of
methyllithium was quenched by addition of water (50 mL).
The organic layer was separated, washed with water (2 ×
20 mL), and dried (Na2SO4). The solvent was removed in
vacuo, and the residue was chromatographed on Al2O3 (hex-
ane–ether, 2:1) to give 0.95 g (50%) of the alcohol 13 ((Z)-
isomer) and 0.48 g (25%) of the ketone 14a and 14b (~5:1),
mp 113–114 °C. The compounds 14a and 14b were sepa-
rated by preparative TLC on silica gel (hexane).
The alcohols 10a, 10b, 13, 14a, or 14b (0.01 mol) was
added to a mixture of dry pyridine (100 mL) and POCl3
(1.0 mL) and stirred at 30–40 °C for 3 h (TLC control). The
reaction mixture was treated with water (100 mL) and ben-
zene (100 mL); the organic layer was separated, washed
with water (3 × 50 mL), and concentrated in vacuo. The res-
idue was chromatographed on a column with Al2O3 in hex-
ane to yield trienes 8a and 8b and dienes 15a and 15b.
(Z)- and (E)-3-Ferrocenylmethylidene-4-methyl-2-phenyl-
1,4-pentadienes (8a) and (8b) from the alcohol (10a)
Yield: 80% (~3:1); orange powder, mp 61–64 °C.
© 2007 NRC Canada

Mendoza et al.
979
7.39–7.93 (5H, m, C6H5). MS m/z: 372 [M]+. Anal. calcd.
for C23H24FeO: C 74.20, H 6.50, Fe 15.00; found: C 74.11,
H 6.63, Fe 14.89.
(Z)-3-Ferrocenylmethylidene-4-methyl-2-phenyl-1,4-
pentadiene (8a)
Yield: 54%; orange powder, mp 68–69 °C. IR (KBr, cm–1):
817, 820, 841, 1005, 1100, 1475, 1642, 1661, 1698, 1927,
1
3032. H NMR (300 MHz, CDCl3) δ: 2.09 (3H, dd, J = 0.6
Dehydration of the alcohols (10a), (10b), and (13) with
AcOH
and 1.2 Hz, CH3), 4.00 (5H, s, C5H5), 4.13 (2H, m, C5H4),
4.35 (2H, m, C5H4), 4.94 (1H, m, J = 0.6 and 1.5 Hz,
CH2=), 4.97 (1H, m, J = 1.2 and 1.5 Hz, CH2=), 5.13 (1H, d,
J = 1.8 Hz, CH2=), 5.86 (1H, d, J = 1.8 Hz, CH2=), 6.46
(1H, s, CH=), 7.24–7.56 (5H, m, C6H5). 13C NMR (75 MHz,
CDCl3) δ: 20.87 (CH3), 68.99, 69.70 (C5H4), 69.04 (C5H5),
81.32 (CipsoFc), 114.85, 114.90 (2 CH2=), 125.11 (CH=),
126.11, 127.67,128.42 (C6H5), 139.06, 139.14, 143.21,
146.48(4C). MS m/z: 354 [M]+. Anal. calcd. for C23H22Fe: C
77.97, H 6.26, Fe 15.77; found: C 78.10, H 6.19, Fe 15.81.
A solution of the alcohols 10a, 10b, or 13 (5 mmol) in
benzene (50 mL) and AcOH (20 mL) was stirred at 20 °C
for 5 h. Then, water (50 mL) was added; the organic layer
was separated, washed with 5% NaHCO3, and concentrated.
The residue was chromatographed on Al2O3 (hexane) to give
the triene 8b.
(E)-3-Ferrocenylmethylidene-4-methyl-2-phenyl-1,4-
pentadienes (8b)
Yield: 74%–82%; orange powder, mp 74–75 °C.
(E)-3-Ferrocenylmethylidene-4-methyl-2-phenyl-1,4-
pentadiene (8b)
(Z)- and (E)-3-Ferrocenyl-2-isopropenyl-1-methyl-1-
phenylallylium tetrafluoroborates (16a and 16b)
These compounds were prepared by the addition of
tetrafluoroboric acid etherate to a solution of the triene 8a or
8b in dry diethyl ether. The crystalline residues that precipi-
tated were filtered off, washed with dry diethyl ether, and
dried in vacuo. The yields of the salts were quantitative. All
operations with solid salts were carried out in an atmosphere
of dry nitrogen.
Yield: 14%; orange powder, mp 74–75 °C. IR (KBr, cm–1):
818, 822, 841, 1003, 1102, 1473, 1645, 1660, 1687, 1924,
1
3034. H NMR (300 MHz, CDCl3) δ: 2.00 (3H, dd, J = 0.9
and 1.5 Hz, CH3), 4.08 (5H, s, C5H5), 4.19 (2H, m, C5H4),
4.41 (2H, m, C5H4), 4.97 (1H, dd, J = 1.5 and 2.4 Hz,
CH2=), 5.12 (1H, dd, J = 0.3 and 1.8 Hz, CH2=), 5.23
(1H, m, J = 0.9 and 2.4 Hz, CH2=), 5.31 (1H, dd, J = 0.3
and 1.8 Hz, CH2=), 5.91 (1H, s, CH=), 7.28–7.38 (5H, m,
C6H5). 13C NMR (75 MHz, CDCl3) δ: 20.42 (CH3), 68.96,
69.35 (C5H4), 69.02 (C5H5), 81.39 (CipsoFc), 114.40, 116.20
(2 CH2=), 127.15 (CH=), 127.43, 127.93,128.87 (C6H5),
141.09, 142.10, 143.83, 150.11(4 C). MS m/z: 354 [M]+.
Anal. calcd. for C23H22Fe: C 77.97, H 6.26, Fe 15.77; found:
C 77.84, H 6.32, Fe 15.58.
Compound (16a)
Yield: 91%; black crystals, mp 219–221 °C. 1H NMR
(300 MHz, CD2CI2) δ: 2.23 (3H, s, CH3), 2.26 (3H, s, CH3),
4.65 (5H, s, C5H5), 4.75 (2H, m, C5H4), 5.09 (2H, m, C5H4),
5.94 (1H, br s, CH2=), 6.07 (1H, br s, CH2=), 7.15–7.56
(5H, m, C6H5), 8.34 (1H, s, CHFc). MS m/z: 442 [M]+.
Anal. calcd. for C23H23BF4Fe: C 62.49, H 5.24, F 17.19, Fe
12.63; found: C 62.34, H 5.31, F 17.27, Fe 12.56.
(Z)- and (E)-3-Ferrocenylmethylidene-4-methyl-2-phenyl-
1,4-pentadienes 8a and 8b from the alcohol (10b)
Yield: 83% (~1:3.6); orange powder, mp 62–65 °C.
Compound (16b)
Yield: 94%; black crystals, mp 226–228 °C. 1H NMR
(300 MHz, CD2CI2) δ: 1.93 (3H, s, CH3), 1.96 (3H, s, CH3),
4.39 (5H, s, C5H5), 4.60 (2H, m, C5H4), 4.88 (1H, m, C5H4),
5.33 (1H, m, C5H4), 5.52 (1H, br s, CH2=), 5.70 (1H, br s,
CH2=), 7.17–7.48 (5H, m, C6H5), 8.20 (1H, s, CHFc). MS
m/z: 442 [M]+. Anal. calcd. for C23H23BF4Fe: C 62.49, H
5.24, F 17.19, Fe 12.63; found: C 62.63, H 5.13, F 17.02, Fe
12.88.
(Z)- and (E)-3-Ferrocenylmethylidene-4-methyl-2-phenyl-
1,4-pentadienes (8a) and (8b) from the diol (13)
Yield: 86% (~2:1); orange powder, mp 62–64 °C.
3-Benzoyl-4-ferrocenyl-2-methyl-1-pentene (15a)
Yield: 74%; orange powder, mp 133–134 °C. IR
(KBr, cm–1): 820, 838, 1001, 1100, 1470, 1653, 1661, 1727,
1
1920, 3030. H NMR (300 MHz, CDCl3) δ: 1.34 (3H, d, J =
7.2 Hz, CH3), 1.74 (3H, dd, J = 0.9 and 1.2 Hz, CH3), 3.33
(1H, m, J = 7.2, 10.5 Hz, CH), 4.12 (5H, s, C5H5), 3.88
(1H, m, C5H4), 3.98 (1H, m, C5H4), 4.00 (1H, m, C5H4),
4.15 (1H, m, C5H4), 3.94 (1H, d, J = 10.5 Hz, CH), 4.94
(2H, m, CH2=), 7.29–7.74 (5H, m, C6H5). MS m/z: 372
[M]+. Anal. calcd. for C23H24FeO: C 74.20, H 6.50, Fe
15.00; found: C 74.12, H 6.31, Fe 15.15.
Isomerization of the tetrafluoroborates (16a) and (16b)
A solution of the salt 16a or 16b (0.44 g, 1 mmol) in dry
CD2CI2 (10 mL) was kept at room temperature for 4. The 1H
NMR spectrum of the solutions contains signals for two
products: 16a and 16b (~1:2).
The reaction of the tetrafluoroborates (16a) and (16b)
with N,N-dimethylaniline
3-Benzoyl-4-ferrocenyl-2-methyl-1-pentene (15b)
Yield: 71%; orange powder, mp 126–127 °C. IR
N,N-Dimethylaniline (1.5 mL) was added with stirring to
a tetrafluoroborate 16a or 16b (0.88 g, 2 mmol). The nearly
black solution gradually turns orange in ~20 min. The reac-
tion products were extracted with benzene (3 × 30 mL); the
combined extract was washed with water (20 mL), 5% HCl
(2 × 20 mL), and water (20 mL); the organic layer was dried
with CaCl2; and the solvent was distilled off. The residue
(KBr, cm–1): 819, 840, 1004, 1103, 1468, 1652, 1660, 1728,
1
1921, 3028. H NMR (300 MHz, CDCl3) δ: 1.26 (3H, d, J =
6.9 Hz, CH3), 2.04 (3H, dd, J = 0.9 and 1.2 Hz, CH3), 2.96
(1H, m, CH), 3.73 (1H, d, J = 9.9 Hz, CH), 4.04 (5H, s,
C5H5), 3.96 (1H, m, C5H4), 4.06 (1H, m, C5H4), 4.10
(1H, m, C5H4), 4.14 (1H, m, C5H4), 5.02 (2H, m, CH2=),
© 2007 NRC Canada

980
Can. J. Chem. Vol. 85, 2007
was chromatographed on a column with Al2O3 (hexane). A
fraction of pure triene 8a or 8b were isolated.
with benzene (3 × 50 mL), 5% aq. NaHCO3, and water and
dried with Na2OS4. The solvent was distilled off, and the
residue was subjected to preparative TLC on silica gel (hex-
ane) to yield 6-ferrocenyl-3-ferrocenylmethylidene-7-
isopropylidene-2-methyl-4,8-diphenyl-nona-1,4,7-trienes
18a–18c and 7-ferrocenyl-4-ferrocenylmethylidene-8-(1-
phenylethylidene)-1,3-dimethyl-5-phenyl-bicyclo[3.3.1]non-
2-ene 19.
Triene (8a) (from the salt 16a)
Yield: 84%; mp 68–69 °C.
Triene (8b) (from the salt 16b)
Yield: 88%; mp 74–75 °C.
6-Ferrocenyl-3-ferrocenylmethylidene-7-isopropylidene-2-
methyl-4,8-diphenyl-nona-1,4,7-triene (18a)
Condensation of the trienes (8a) and (8b) with N-
phenylmaleimide
Yield: 34%; Rf = 0.63, orange powder, mp 164–165 °C.
A solution of the triene 8a (or 8b) (0.35 g, 1 mmol) and
N-phenylmaleimide (0.2 g, 1.24 mmol) in toluene (50 mL)
was refluxed for 3 h and concentrated. The residue was
chromatographed on Al2O3 (hexane – dichloromethane, 3:1)
to give 0.37 g (70%) (from 8a) or 0.40 g (75%) (from 8b) of
the adducts 17 as a mixture of two isomers 17a and 17b
(~3:1, NMR data), yellow crystals, mp 188–200 °C. The iso-
mers were separated by preparative TLC on Al2O3 (hexane–
benzene, 1:1).
IR (KBr, cm–1): 820, 998, 1007, 1105, 1134, 1179, 1379,
1
1451, 1518, 1641, 1676, 1684, 2879, 2923, 3078. H NMR
(300 MHz, CDCI3) δ: 1.74 (3H, br s, CH3), 1.90 (3H, s,
CH3), 2.07 (3H, m, J = 0.6 and 0.9 Hz, CH3), 3.69 (5H, s,
C5H5), 4.02 (5H, s, C5H5), 4.01 (1H, m, C5H4), 4.15 (2H, m,
C5H4), 4.37 (2H, m, C5H4), 4.48 (1H, d, J = 10.8 Hz,
CHFc), 4.57 (2H, m, C5H4), 4.70 (1H, m, C5H4), 4.83
(1H, m, CH2=), 4.93 (1H, m, CH2=), 4.98 (1H, m, CH2=),
5.28 (1H, m, CH2=), 5.49 (1H, s, CH=), 5.86 (1H, d, J =
10.8 Hz, CH=), 6.88 (2H, m, C6H5), 7.14–7.51 (8H, m,
C6H5). 13C NMR (75 MHz, CDCl3) δ: 21.95, 23. 34, 32,52
(3 CH3), 41.74 (CH), 66.63, 66.81, 67.01, 67.23, 67.49,
67.89, 68.48, 69.34 (2 C5H4), 68.62, 69.17 (2 C5H5), 83.25,
90.34 (2 CipsoFc), 117.43, 118.21 (2 CH2=), 124.31, 130.10
(2 CH=), 126.79, 126.99, 127.45, 128.32, 128.47, 128.98 (2
C6H5), 125.83, 131.87, 132.29, 134,09, 134.73, 139.91,
140.95, 143.54 (8C). MS m/z: 708 [M]+. Anal. calcd. for
C46H44Fe2: C 77.97, H 6.26, Fe 15.77; found: C 78.12, H
6.18, Fe 15.81.
Endo-adduct (17a)
Yield: 50%; yellow powder, mp 208–209 °C. IR
(KBr, cm–1): 770, 826, 1002, 1035, 1102, 1157, 1186, 1385,
1
1436, 1498, 1629, 1685, 1711, 1776, 2872, 2937, 3081. H
NMR (300 MHz, CDCI3) δ: 1.64 (3H, m, J = 0.9 Hz, CH3),
2.86 (1H, dd, J = 6.0 and 12.0 Hz, CH2), 3.18 (1H, dd, J =
7.8 and 12.0 Hz, CH2), 3.41 (1H, m, CH), 3.74 (1H, dd, J =
1.5 and 9.0 Hz, CH), 4.18 (5H, s, C5H5), 4.10 (2H, m,
C5H4), 4.27 (2H, m, C5H4), 4.25 (1H, d, J = 1.5 Hz, CHFc),
4.93 (1H, m, J = 0.9 Hz, CH2=), 5.00 (1H, m, CH2=), 7.02–
7.05 (2H, m, C6H5), 7.12–7.49 (8H, m, C6H5). MS m/z: 527
[M]+. Anal. calcd. for C33H29FeNO2: C 75.15, H 5.54, Fe
10.59, N 2.65; found: C 74.91, H 5.63, Fe 10.69, N 2.59.
6-Ferrocenyl-3-ferrocenylmethylidene-7-isopropylidene-2-
methyl-4,8-diphenyl-nona-1,4,7-triene (18b)
Yield: 21%; Rf = 0.57, orange powder, mp 171–172 °C.
IR (KBr, cm–1): 818, 1001, 1006, 1101, 1140, 1182, 1383,
Exo-adduct (17b)
1
1448, 1521, 1640, 1660, 1681, 2882, 2936, 3085. H NMR
Yield: 15%; yellow powder, mp 201–202 °C. IR
(KBr, cm–1): 767, 821, 1001, 1027, 1102, 1148, 1186, 1387,
(300 MHz, CDCI3) δ: 1.63 (3H, m, J = 0.9 Hz, CH3), 1.82
(3H, s, CH3), 2.12 (3H, m, CH3), 3.74 (5H, s, C5H5), 4.05
(5H, s, C5H5), 3.95 (2H, m, C5H4), 4.08 (1H, m, C5H4), 4.12
(1H, m, C5H4), 4.20 (2H, m, C5H4), 4.35 (2H, m, C5H4),
4.42 (1H, d, J = 10.5 Hz, CHFc), 4.72 (1H, m, CH2=), 5.14
(1H, m, CH2=), 5.32 (1H, m, CH2=), 5.57 (1H, s, CH=),
5.86 (1H, m, CH2=), 6.05 (1H, d, J = 10.5 Hz, CH=), 7.12–
7.61 (10H, m, 2 C6H5). 13C NMR (75 MHz, CDCl3) δ:
21.76, 23. 44, 32.36 (3 CH3), 41.85 (CH), 66.58, 66.63,
67.19, 67.34, 67.09, 67.57, 68.29, 69.07 (2 C5H4), 68.60,
69.23 (2 C5H5), 83.28, 90.37 (2 CipsoFc), 117.31, 118.28 (2
CH2=), 124.48, 130.15 (2 CH=), 126.83, 127.03, 127.34,
128.49, 128.53, 128.74 (2 C6H5), 125.57, 130.48, 132.13,
134,03, 134.58, 139.84, 140.66, 143.32 (8 C). MS m/z: 708
[M]+. Anal. calcd. for C46H44Fe2: C 77.97, H 6.26, Fe 15.77;
found: C 77.85, H 6.29, Fe 15.66.
1
1435, 1501, 1630, 1685, 1714, 1766, 2875, 2939, 3080. H
NMR (300 MHz, CDCI3) δ: 1.88 (3H, m, J = 1.2 Hz, CH3),
2.75 (1H, dd, J = 9.6 and 15.3 Hz, CH2), 3.07 (1H, dd, J =
8.1 and 15.3 Hz, CH2), 3.24 (1H, m, CH), 3.37 (1H, dd, J =
5.4 and 9.6 Hz, CH), 4.04 (5H, s, C5H5), 4.11 (2H, m,
C5H4), 4.14 (1H, m, C5H4), 4.27 (1H, m, C5H4), 4.47 (1H, d,
J = 5.4 Hz, CHFc), 5.01 (1H, m, J = 1.2 Hz, CH2=), 5.10
(1H, m, CH2=), 7.09–7.13 (2H, m, C6H5), 7.23–7.46 (8H, m,
C6H5). 13C NMR (75 MHz, CDCl3) δ: 22.86 (CH3), 28.57
(CH2), 39.79, 42.21, 48.06 (3 CH), 67.07, 68.58 (C5H4),
69.21 (C5H5), 83.55 (CipsoFc), 117.29 (CH2=), 126.70,
126.87, 127.66, 128.11, 128.49, 128.94 (2 C6H5), 131.71,
134.86, 140.39, 142.95, 144.54(5 C), 177.42, 178.53 (2
C=O).
MS m/z: 527 [M]+. Anal. calcd. for C33H29FeNO2:
C 75.15, H 5.54, Fe 10.59, N 2.65; found: C 75.29, H 5.43,
Fe 10.42, N 2.71.
6-Ferrocenyl-3-ferrocenylmethylidene-7-isopropylidene-2-
methyl-4,8-diphenyl-nona-1,4,7-triene (18c)
Dimerization of (Z)- and (E)-3-Ferrocenylmethylidene-4-
methyl-2-phenyl-1,4-pentadienes (8a) and (8b)
A solution of the triene 8a (or 8b) (0.70 g, 2 mmol) in
glacial acetic acid (50 mL) and CF3COOH (5 mL) was
refluxed for 4 h, cooled to ambient temperature, and diluted
with water (100 mL). The reaction products were extracted
Yield: 9%; Rf = 0.49, orange powder, mp 158–159 °C. IR
(KBr, cm–1): 822, 1003, 1011, 1101, 1131, 1181, 1390,
1
1447, 1527, 1643, 1661, 1678, 2881, 2926, 3071. H NMR
(300 MHz, CDCI3) δ: 1.86 (3H, br s, CH3), 1.92 (3H, m,
CH3), 2.06 (3H, s, CH3), 4.03 (5H, s, C5H5), 4.11 (5H, s,
© 2007 NRC Canada

Mendoza et al.
981
Table 2. Crystal data, data collection, and refinement parameters for compounds 6, 9, 11a, and 13.
Crystal
6
9
11a
13
Empirical formula
C36H40Fe2
C22H20FeO3
C23H24FeO
C23H26FeO2
Formula mass
584.38
388.23
372.27
390.29
Color, habit
Orange prism
0.346 × 0.064 × 0.048
Monoclinic
P21/c
Dark red prism
0.60 × 0.50 × 0.35
Monoclinic
P21/n
Yellow prism
0.30 × 0.16 × 0.13
Monoclinic
P21/n
Orange prism
0.392 × 0.174 × 0.062
Monoclinic
Crystal dimensions (mm)
Crystal system
Space group
P21/n
Z
4
4
4
4
a (Å)
b (Å)
c (Å)
α (°)
β (°)
γ (°)
14.3336(12)
13.7797(11)
15.9865(13)
90
114.784(2)
90
–17 ≤ h ≤ 17;
–16 ≤ k ≤ 16;
–19 ≤ l ≤ 19
298(2)
2866.7(4)
1.354
9.539(2)
17.236(4)
11.120(2)
90
93.816(14)
90
–1 ≤ h ≤ 11;
–1 ≤ k ≤ 21;
–13 ≤ l ≤ 13
298(2)
1824.2(7)
1.413
7.6853(4)
14.0988(8)
17.177(1)
90
93.750(1)
90
–9 ≤ h ≤ 9;
–16 ≤ k ≤ 16;
–20 ≤ l ≤ 20
291(2)
1857.3(2)
1.331
13.3329(10)
8.7769(6)
17.2372(13)
90
98.362(2)
90
–16 ≤ h ≤ 13;
–10 ≤ k ≤10;
–20 ≤l ≤20
298(2)
1994.2(2)
1.300
Collection ranges
Temperature (K)
Volume (Å3)
Dcalcd. (Mg m–3)
Radiation
Mo Kα
Mo Kα
Mo Kα
Mo Kα
(λ = 0.71073 Å)
1.035
(λ = 0.71073 Å)
0.845
(λ = 0.71073 Å)
0.819
(λ = 0.71073 Å)
0.769
Absorption coeff.(µ) (mm–1)
F(000)
1232
808
784
824
θ range for data collection (°)
Observed reflections
Independent reflections
2.04–25.06
23021
5054 (Rint = 0.0836)
2.18–26.00
4540
3578 (Rint = 0.0444)
1.87–25.00
14976
1.81 – 25.35
11909
3267 (Rint = 0.0442) 3646 (Rint = 0.0562)
Data/restraints/parameters
Maximum shift/error
Goodness-of-fit on F2
Final R indices [I > σ(I)]
5054/0/348
0.000
1.095
R1 = 0.0721,
wR2 = 0.1424
3578/0/201
0.000
1.051
R1 = 0.0434,
wR2 = 0.1338
3267/0/228
0.000
0.909
R1 = 0.0374,
wR2 = 0.0809
3646/0/287
0.001
0.893
R1 = 0.0497,
wR2 = 0.0768
R indices (all data)
R1 = 0.1042,
wR2 = 0.1554
R1 = 0.0513,
wR2 = 0.1370
R1 = 0.0499,
wR2 = 0.0840
R1 = 0.0876,
wR2 = 0.0864
C5H5), 3.96–4.20 (8H, m, 2 C5H4), 4.55 (1H, d, J = 11.1 Hz,
CHFc), 4.87 (1H, m, CH2=), 5.00 (1H, m, CH2=), 5.02
(1H, m, CH2=), 5.35 (1H, m, CH2=), 5.52 (1H, s, CH=),
5.91 (1H, d, J = 11.1 Hz, CH=), 7.15–7.43 (10H, m, 2
C6H5). 13C NMR (75 MHz, CDCl3) δ: 21.85, 23. 37, 32,53
(3 CH3), 41.91 (CH), 66.84, 66.92, 67.26, 67.49, 67.12,
67.64, 68.49, 69.16 (2 C5H4), 68.71, 69.32 (2 C5H5), 83.34,
90.43 (2 CipsoFc), 117.43, 118.32 (2 CH2=), 122.57, 129.87
(2 CH=), 125.29, 126.37, 127.02, 128.31, 128.58, 128.63 (2
C6H5), 124.16, 129.11, 130.88, 132.41, 134.42, 139.76,
140.52, 143.64 (8 C). MS m/z: 708 [M]+. Anal. calcd. for
C46H44Fe2: C 77.97, H 6.26, Fe 15.77; found: C 77.79, H
6.37, Fe 15.95.
(5H, s, C5H5), 4.23 (5H, s, C5H5), 4.13 (2H, m, C5H4), 4.18
(2H, m, C5H4), 4.21 (2H, m, C5H4), 4.31 (1H, m, C5H4),
4.49 (1H, m, C5H4), 6.12 (1H, q, J = 1.2 Hz, CH=), 6.29
(1H, s, CH=), 7.08–7.63 (10H, m, 2 C6H5). 13C NMR
(75 MHz, CDCl3) δ: 23.05, 26. 14, 29.32 (3 CH3), 39.18,
40.14 (2 CH2), 43.18 (CH), 43.56, 52.08 (2C), 68.63, 68.79,
69.52, 69.70 (2 C5H4), 68.84, 69.61 (2 C5H5), 79.24, 83.41
(2 CipsoFc), 119.23, 126.63 (2 CH=), 127.24, 127.43, 127.64,
127.83, 127.95, 128.56 (2 C6H5), 121.94, 129.18, 133.07,
142.10, 143.48, 144.21 (6C). MS m/z: 708 [M]+. Anal.
calcd. for C46H44Fe2: C 77.97, H 6.26, Fe 15.77; found: C
77.90, H 6.31, Fe 15.85.
Condensation of the tetrafluoroborates (16a) and (16b)
with the trienes (8a) and (8b)
7-Ferrocenyl-4-ferrocenylmethylidene-8-(1-phenylethyl-
idene)-1,3-dimethyl-5-phenyl-bicyclo[3.3.1]non-2-ene (19)
Yield: 14%; Rf = 0.71, yellow powder, mp 182–183 °C. IR
(KBr, cm–1): 769, 1001, 1010, 1108, 1125, 1179, 1392,
The triene 8a (or 8b) (0.35 g, 1 mmol) was added to a so-
lution of the tetrafluoroborate 16a (or 16b) (0.49g,
1.1 mmol) in dichloromethane (60 mL), and the mixture was
stirred at 20 °C for 1 h. N,N-Dimethylaniline (0.6 mL) was
then added, and stirring was continued for 30 min. The reac-
tion mixture was washed with water, 5% HCl, and water and
dried with CaCl2. The solvent was removed in vacuo, and
the reaction products were separated by TLC on SiO2 (hex-
1
1442, 1531, 1640, 1654, 1660, 2877, 2929, 3070. H NMR
(300 MHz, CDCI3) δ: 1.51 (3H, s, CH3), 1.81 (3H, d, J =
1.2 Hz, CH3), 1.92 (3H, s, CH3), 2.35 (1H, dd, J = 5.7 and
13.2 Hz, CH2), 2.54 (2H, s, CH2), 2.73 (1H, dd, J = 3.6 and
13.2 Hz, CH2), 3.95 (1H, dd, J = 3.6 and 5.7 Hz, CH), 4.14
© 2007 NRC Canada

982
Can. J. Chem. Vol. 85, 2007
8. E. Stankovic, S. Toma, R.V. Boxel, I. Asselberghs, and A.
Persoons. J. Organomet. Chem. 637–639, 426 (2001).
9. L.M. Tolbert, X. Zhao, Y. Ding, and L.A. Bottomley. J. Am.
Chem. Soc. 117, 12891 (1995).
ane). The following compounds were obtained: compounds
18a–18c (42%, ~3:2:1), compound 19 (28%), and polymeric
products.
10. B. Bildstein, W. Skibar, M. Schweiger, H. Kapacka, and K.
Compound (18a)
Yield: 21%; Rf = 0.63, orange powder, mp 163–165 °C.
Wurst. J. Organomet. Chem. 622, 135 (2001).
11. A.E. Kaifer and S. Mendoza. Comprehensive supramolecular
chrmistry I. Edited by G.W. Gokel. Pergamon, Oxford. 1996.
12. A. Peruga, J.A. Mata, D. Sainz, and E. Periz. J. Organomet.
Chem. 637–639, 191 (2001).
Compound (18b)
Yield: 14%; Rf = 0.57, orange powder, mp 171–172 °C.
13. A.N. Pushin, E.I. Klimova, and V.A. Sazonova. Russ. J. Gen.
Compound (18c)
Yield: 9%; Rf = 0.49, orange powder, mp 158–159 °C.
Chem. 59, 1102 (1989).
14. E.G. Perevalova, E.I. Klimova, V.V. Kruchkova, and A.N.
Pushin. Russ. J. Gen. Chem. 59, 873 (1989).
15. V.N. Postnov, E.I. Klimova, A.N. Pushin, and N.N.
Meleshonkova. Metalloorg. Khim. 4, 116 (1991).
16. E.I. Klimova, A.N. Pushin, and V.A. Sazonova. J. Organomet.
Chem. 270, 319 (1984).
17. E.I. Klimova, L. Ruiz Ramirez, M. Martinez Garcia, P. G.
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Perez, and M.G. Martinez. J. Organomet.Chem. 689, 2503
(2004).
20. E.I. Klimova, T.B. Klimova, M. Martínez García, and L. Ruíz
Ramírez. J. Organomet. Chem. 579, 30 (1999).
21 E.I. Klimova, T.B. Klimova, M. Martínez García, and L. Ruíz
Ramírez. Mendeleev Commun. 233 (1998).
22. E.I. Klimova, M. Martínez García, T. Klimova, and J.M.
Mendez Stivalet. J. Organomet. Chem. 602, 105 (2000).
23. E.I. Klimova, T. Klimova, J.M. Mendez Stivalet, C.T. Alvarez,
R.A. Toscano, S.O. Hernandez, L. Ruíz Ramírez, L.V.
Bakinovscky, and M.G. Martínez. Eur. J. Org. Chem. 1714
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Compound (19)
Yield: 28%; Rf = 0.71, yellow powder, mp 182–183 °C.
X-ray crystallographic studies
The unit-cell parameters and the X-ray diffraction intensi-
ties were recorded on a Bruker Smart Apex CCD area detec-
tor/ω diffractometer (compounds 6, 11a, and 13) and on a
Siemens P4 diffractometer (compound 9). The principal geo-
metrical parameters of the molecules 6, 9, 11a, and 13 are
listed in Table 1. The crystallographic data, the parameters
of the X-ray diffraction experiment, and refinements are
listed in Table 2. The structure of compounds 6, 9, 11a, and
13 were solved by the direct method [SHELXS-97, (30)]
and refined using full-matrix least-squares on F2.2
Acknowledgements
This work was supported by the grant DGAPA–UNAM
(Mexico, grant IN 207606). Thanks are due to E.A. Vazquez
Lopez, R.I. Del Villar Morales, M. Gutierrez Franco, and
G.A. Duarte Lisi for their technical assistance.
24. E.I. Klimova, T.B. Klimova, J.M. Mendez Stivalet, R.A.
Toscano, C.T. Alvarez, and M. Martínez García. J. Organomet.
Chem. 689, 3232 (2004).
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2 Supplementary data for this article are available on the journal Web site (canjchem.nrc.ca) or may be purchased from the Depository of Un-
published Data, Document Delivery, CISTI, National Research Council Canada, Ottawa, ON K1A 0R6, Canada. DUD 5210. For more in-
formation on obtaining material, refer to cisti-icist.nrc-cnrc.gc.ca/irm/unpub_e.shtml. CCDC 272999 for compound 6, 273000 for compound
9, 273001 for compound 11a, and 273002 for compound 13 contain the crystallographic data for this manuscript. These data can be ob-
tained, free of charge, via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax +44 1223 336033; or deposit@ccdc.cam.ac.uk).
© 2007 NRC Canada