2,3-Diferrocenylcyclopropenone in the reaction with organomagnesium compounds

Article abstract of DOI:10.1023/B:RUCB.0000037852.21475.1a

The reactions of 2,3-diferrocenylcyclopropenone with ethyl- and benzylmagnesium chlorides afford 3,3-diethyl- and 3,3-dibenzyl-1,2- diferrocenylcyclopropenes along with products of nucleophilic opening of the three-membered ring: α,β-unsaturated and satur

Full text of DOI:10.1023/B:RUCB.0000037852.21475.1a

834
Russian Chemical Bulletin, International Edition, Vol. 53, No. 4, pp. 834—841, April, 2004
2,3ꢀDiferrocenylcyclopropenone in the reaction
with organomagnesium compounds
E. I. Klimova,aꢀ T. Klimova,a L. Ruiz Ramirez,a J. M. Mendez Stivalet,a
S. Hernandez Ortega,b and M. Martínez Garcíab
aDepartment of Chemistry, National Autonomous University of Mexico,
Mexico, C. P. 04510, Mexico.*
Fax: +52 (55) 5622 5371. Eꢀmail: klimova@servidor.unam.mx
bInstitute of Chemistry, National Autonomous University of Mexico,
Mexico, C. P. 04510, Mexico.**
Fax: +52 (55) 5616 2203
The reactions of 2,3ꢀdiferrocenylcyclopropenone with ethylꢀ and benzylmagnesium chloꢀ
rides afford 3,3ꢀdiethylꢀ and 3,3ꢀdibenzylꢀ1,2ꢀdiferrocenylcyclopropenes along with products
of nucleophilic opening of the threeꢀmembered ring: α,βꢀunsaturated and saturated ketones
(cisꢀ1,2ꢀdiferrocenylpentꢀ1ꢀenꢀ3ꢀone and cisꢀ1,2ꢀdiferrocenylꢀ4ꢀphenylbutꢀ1ꢀenꢀ3ꢀone,
4,5ꢀdiferrocenylheptanꢀ3ꢀone, and 3,4ꢀdiferrocenylꢀ1,5ꢀdiphenylpentanꢀ2ꢀone). The prodꢀ
ucts of insertion of intermediate diferrocenyl(vinyl)carbene at one of the σꢀbonds of the
starting 2,3ꢀdiferrocenylcyclopropenone were also isolated: 4ꢀ(2ꢀoxoꢀ1ꢀferrocenylbutyl)ꢀ and
4ꢀ(2ꢀoxoꢀ3ꢀphenylꢀ1ꢀferrocenylpropyl)ꢀ2,3,4ꢀtriferrocenylcyclobutenones. 3,3ꢀDibenzylꢀ1,2ꢀ
diferrocenylcyclopropene and one of the diastereomers of 4,5ꢀdiferrocenylheptanꢀ3ꢀone were
studied by Xꢀray diffraction analysis.
Key words: ferrocene, 2,3ꢀdiferrocenylcyclopropenone, 1,2ꢀdiferrocenylcyclopropenes,
diferrocenyl(vinyl)carbenes, 2,3,4ꢀtriferrocenylcyclobutenones.
Compounds of the cyclopropenone series are of interꢀ
and stereochemistry of transformations of ferrocenylcycloꢀ
est due to their pseudoꢀaromatic nature1,2 and high strain
energy, planarity and kinetic lability1—3 of the cycloꢀ
propenone structure, and potential practical appliꢀ
cations. 2,3ꢀDiphenylcyclopropenone was the first cycloꢀ
propenone derivative described in the literature.4 Then
many works described syntheses and studies of the reacꢀ
tivity of arylꢀ and alkylꢀsubstituted cyclopropenones and
considered the use of these compounds in organic synꢀ
thesis.5—10
propenones is of doubtless interest. The latter, if accesꢀ
sible, could be the starting substances for syntheses of
many useful compounds of the ferrocene series, which
combine olefinic fragments with functional groups in the
same molecule.
We succeeded in substantial increasing the yield of
cyclopropenone 1 (to 90%) by the alkylation of ferrocene
with tetrachlorocyclopropene at 20 °С in СН2Cl2 using a
smaller amount of AlCl3 (Scheme 1).
Ferrocenylꢀsubstituted analogs of arylcyclopropenones
remain unstudied up to date, although 2,3ꢀdiferrocenylꢀ
cyclopropenone (1) has been isolated for the first time as
early as in 1975 by the alkylation of ferrocene with
tetrachlorocyclopropene at low temperature in the presꢀ
ence of AlCl3 in ~7% yield.11 The main reaction product
was the 1,2,3ꢀtriferrocenylcyclopropenylium salt. At the
same time, the influence of ferrocenyl fragments on regioꢀ
Scheme 1
Fc = C5H5FeC5H4—
* Facultad de Química, Universidad Nacional Autónoma de
México, Cd. Universitaria, Coyoacán, C. P. 04510, México
D. F., México.
** Instituto de Química, Universidad Nacional Autónoma de
México, Cd. Universitaria, Coyoacán, C. P. 04510, México
D. F., México.
In this work, we studied the reactions of cycloꢀ
propenone 1 with organomagnesium compounds, viz.,
ethylꢀ and benzylmagnesium chlorides (EtMgCl and
BnMgCl, respectively).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 798—805, April, 2004.
1066ꢀ5285/04/5304ꢀ0834 © 2004 Plenum Publishing Corporation

2,3ꢀDiferrocenylcyclopropenone
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
835
Table 1. Bond lengths (d) and bond (ω) and
torsion (α) angles in molecules 4а and 6
We found that cyclopropenone 1 reacts with excess
EtMgCl to yield a mixture of several products, the main
of which being 1,2ꢀdiferrocenylꢀ3,3ꢀdiethylcyclopropene
(2), 1,2ꢀdiferrocenylpentꢀ1ꢀenꢀ3ꢀone (3), 4,5ꢀdiferroꢀ
cenylheptanꢀ3ꢀone (4), and 4ꢀ(2ꢀoxoꢀ1ꢀferrocenylbutyl)ꢀ
2,3,4ꢀtriferrocenylcyclobutenone (5) (Scheme 2).
Bond
d/Å
Compound 4а
С(11)—С(22)
С(21)—С(22)
С(12)—С(13)
С(1)—С(21)
С(21)—С(23)
С(22)—С(25)
О(1)—С(25)
С(25)—С(26)
1.468(7)
1.567(5)
1.428(8)
1.570(7)
1.539(8)
1.485(8)
1.191(6)
1.469(7)
Scheme 2
Compound 6
С(11)—С(13)
С(11)—С(12)
С(12)—С(13)
С(1)—С(11)
С(13)—С(14)
С(12)—С(24)
С(12)—С(25)
1.286(3)
1.499(3)
1.493(3)
1.444(3)
1.444(3)
1.532(3)
1.534(3)
Bond angle
ω/deg
Compound 4а
С(11)—С(22)—С(25)
С(25)—С(22)—С(21)
С(22)—С(21)—С(1)
С(23)—С(21)—С(22)
О(1)—С(25)—С(22)
О(1)—С(25)—С(26)
С(11)—С(22)—С(21)
С(1)—С(21)—С(23)
112.4(5)
110.5(5)
107.4(4)
109.1(5)
120.4(5)
120.9(7)
112.3(4)
112.2(5)
The reaction with BnMgCl occurs similarly to form
cyclopropene 6, α,βꢀunsaturated ketone 7, saturated keꢀ
tone 8, and cyclobutenone 9. An unexpected reaction
product is 2ꢀhydroxyꢀ3ꢀoxoꢀ1,2ꢀdiferrocenylꢀ1,2,3,4ꢀ
tetrahydronaphthalene (10) (Scheme 3).
Scheme 3
Compound 6
С(13)—С(11)—С(12)
С(13)—С(12)—С(11)
С(11)—С(13)—С(12)
С(53)—С(52)—С(51)
С(52)—С(53)—С(51)
С(53)—С(51)—С(52)
C(24)—C(12)—C(11)
С(24)—С(12)—С(25)
C(13)—C(12)—C(25)
С(64)—С(52)—С(65)
64.28(19)
50.90(15)
64.82(19)
50.90(15)
64.14(15)
64.94(19)
120.2(2)
111.4(2)
120.8(2)
111.7(2)
Torsion angle
α/deg
Compound 6
С(11)—С(12)—С(24)—С(26) –95.2(3)
С(51)—С(52)—С(65)—С(66) 25.9(4)
С(11)—С(12)—С(25)—С(32) –33.9(4)
С(51)—С(52)—С(64)—С(72) –155.4(2)
The spatial configuration of one of cyclopropenes,
viz., 3,3ꢀdibenzylꢀ1,2ꢀdiferrocenylcyclopropene 6, was
confirmed by spectral data and Xꢀray diffraction analysis
of single crystals obtained by crystallization from hexane
(Tables 1 and 2). The general view of molecule 6 is shown
in Fig. 1, a. The threeꢀmembered ring in structure 6 is an
isosceles triangle. The С=С bond length (d = 1.286(3) Å)
The structures of compounds 2—10 were established
by the data of 1Н and 13С NMR spectroscopy (see Experiꢀ
mental).

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Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Klimova et al.
C(28)
C(29)
C(34)
C(35)
C(37)
C(33)
C(12)
C(36)
C(27)
a
C(25)
C(32)
C(26)
C(24)
C(30)
C(31)
C(13)
C(11)
C(18)
C(14)
C(5)
C(4)
C(17)
C(16)
C(1)
C(2)
C(3)
C(23)
Fe(2)
C(15)
Fe(1)
C(10)
C(6)
C(19)
C(20)
C(22)
C(21)
C(7)
C(9)
C(8)
C(76)
C(77)
C(28)
C(29)
C(30)
C(75)
b
C(34)
C(35)
C(37)
C(27)
C(25)
C(26)
C(33)
C(36)
C(74)
C(32)
C(72)
C(12)
C(13)
C(14)
C(24)
C(11)
C(65)
C(31)
C(73)
C(18)
C(64)
C(52)
C(66)
C(17)
C(5)
C(1)
C(71)
C(70)
C(47)
C(42)
C(23)
C(19)
C(53)
C(55)
C(4)
Fe(1)
C(8)
Fe(2)
C(51)
C(60)
C(61)
C(16)
C(10)
C(9)
C(15)
C(21)
C(54)
C(58)
C(2)
C(59)
C(46)
C(50)
C(3)
C(20)
Fe(4)
C(62)
Fe(3)
C(49)
C(43)
C(44)
C(7)
C(63)
Fig. 1. General view of a 3,3ꢀdibenzylꢀ1,2ꢀdifferrocenylcyclopropene (6) molecule (a) and molecular structures of two independent
molecules (b).
and the value of the ω acute angle at С(12) (50.90(15)°)
differ slightly from the corresponding values for 3ꢀarylꢀ3ꢀ
ferrocenylcyclopropenes.12,13 Substituted cyclopentaꢀ
dienyl rings of the ferrocene fragments lie in the plane of
the small cycle. The Fe—С bond lengths and geometry of
the ferrocene sandwiches are the same as those in related
compounds.12,13 The unit cell of the crystal structure of
compound 6 contains two independent differrocenylꢀ
cyclopropene molecules, whose geometric parameters are
the same, except for rotational angles of the phenyl rings
about the Сsp3—Сsp3 ordinary bonds (see torsion angles in
Table 1 and Fig. 1, b).
As follows from the data of 1Н and 13С NMR spectroꢀ
scopy, compounds 3 and 7 are formed as one geometꢀ

2,3ꢀDiferrocenylcyclopropenone
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
837
Table 2. Crystallographic data and Xꢀray diffraction parameters for compounds 4а and 6
Parameter
4a
6
Molecular formula
С27Н30Fe2О
482.21
С37Н32Fe2
588.33
291(2)
Molecular weight/g mol–1
Temperature/K
291(2)
Crystal system
Space group
Monoclinic
Р21
Triclinic
Р–1
а/Å
b/Å
с/Å
α/deg
11.0169(8)
7.8226(5)
13.1321(9)
90.0
102.3290(10)
90.0
10.4144(6)
10.4124(6)
27.457(2)
81.120(1)
80.692(1)
71.093(1)
2763.0(3)
4
β/deg
γ/deg
V/Å3
1105.63(13)
2
Z
dcalc/g cm–3
1.448
1.328
1.414
1.075
Absorption coefficient/mm–1
F(000)
504
1224
Radiation
λ/Å
Monochromator
θ/deg
MoꢀKα
0.71073
Graphite
1.59—25.00
9069
МоꢀКα
0.71073
Graphite
2.08—25.00
22799
Total number of reflections
Number of independent reflections with R(I > 2σ(I ))
3864
9737
R1
wR2
0.0390
0.0749
0.06(2)
0.0351
0.0384
0.0634
—
Parameter of absolute structure
Rint
Number of refined parameters
Weighing scheme
0.0425
703
273
w = 1/[σ (F0 ) + (0.0305P)2],
w = 1/[σ (F0 ) + (0.0190P)2],
2
2
2
2
where Р = (F02 + 2Fс )/3
where Р = (F02 + 2Fс )/3
2
2
GOOF (fullꢀmatrix leastꢀsquares method against F 2)
Residual electron density/eÅ–3, ρ /ρ
1.033
–0.183/0.478
0.829
–0.226/0.379
min max
ric isomer, most likely, with cisꢀoriented ferrocene
groups,14,15 and compounds 4 and 8 exist as mixtures of
two diastereomeric forms 4а,b and 8a,b, respectively, in
a ratio of ~3 : 1 (see Experimental). Diastereomeric
heptanones 4а and 4b were separated by preparative TLC
on SiO2. The spatial structure of isomer 4а was estabꢀ
lished by Xꢀray diffraction analysis of a single crystal isoꢀ
lated by crystallization from hexane (see Tables 1 and 2,
Fig. 2). It follows from the Xꢀray diffraction data that
compound 4а has a structure of 4R,5Sꢀdiferrocenylꢀ
heptanꢀ3ꢀone. By analogy, we ascribed the erythroꢀconꢀ
figuration to compound 8а. Spectral identification of keꢀ
tones 4а,b and 8а,b was not difficult, because positions of
tuted cyclopentadienyl rings, signals of the methyl (in 5)
and methylene (in 9) groups, and one signal from each
methine proton. Each 13С NMR spectrum exhibits four
signals of quaternary C atoms of the ferrocene fragments
of molecules 5 and 9, two signals of C atoms of the carꢀ
bonyl group, and the corresponding number of signals of
the quaternary C and Cipso atoms. The mass spectra of
compounds 5 and 9 contain peaks of molecular ions
with m/z 874 and 936, respectively, which also indiꢀ
cates their dimeric nature and confirms the structure proꢀ
posed.
The structure of compound 10 was determined from
1
the data of mass spectrometry, IR spectroscopy, and Н
all signals in the Н and 13С NMR spectra, their multiꢀ
and 13С spectroscopy. The molecule contains the carboꢀ
nyl and hydroxyl groups, two ferrocene substituents,
orthoꢀdisubstituted phenyl fragment, and methylene and
methine groups.
1
plicities, and integral intensities differ distinctly.
Bright violet compounds 5 and 9 were isolated in inꢀ
significant amounts (~6%) as one diastereomeric form.
1
Their structures also follow from the data of Н and 13С
Thus, the results obtained show that the reaction of
2,3ꢀdiferrocenylcyclopropenone 1 with organomagnesium
compounds includes three main processes: (1) with reꢀ
tention of the small threeꢀmembered ring, (2) with nuꢀ
cleophilic opening of the cyclopropenone ring, and
1
NMR spectroscopy. For instance, the Н NMR spectra
of compounds 5 and 9 contain signals of four unsubstituted
cyclopentadienyl ferrocene rings along with the corꢀ
responding number of signals of protons of the substiꢀ

838
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Klimova et al.
(3) with subsequent ring closure of cyclopropenone reꢀ
lated to ring extension and formation of triferrocenylꢀ
substituted cyclobutenone structures. The second process
is prevailing.
3,3ꢀDiethylꢀ and 3,3ꢀdibenzylꢀ1,2ꢀdiferrocenylcycloꢀ
propenes 2 and 6 are formed, most likely, by the interacꢀ
tion of intermediate magnesium alkoxides 11а,b with the
second RMgCl molecule (Scheme 4).
C(19)
C(18)
C(14)
C(13)
C(12)
C(17)
C(20)
Fe(1)
C(15)
C(16)
C(11)
C(22)
C(24)
Scheme 4
O(1)
C(21)
C(23)
C(6)
C(25)
C(26)
C(1)
C(27)
C(2)
C(10)
C(5)
C(4)
Fe(2)
C(9)
C(7)
C(3)
C(8)
R = Et (2, 11a); Bn (6, 11b)
Similar processes, resulting in the complete replaceꢀ
ment of the carbonyl group by hydrocarbon radicals, have
Fig. 2. Molecular structure of R,Sꢀ4,5ꢀdiferrocenylheptanꢀ
3ꢀone (4а).
Scheme 5

2,3ꢀDiferrocenylcyclopropenone
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
839
ferrocene (5.6 g, 0.03 mol) and tetrachlorocyclopropene (3.6 g,
0.02 mol) in anhydrous CH2Cl2 (200 mL). Stirring was continꢀ
ued for 1 h at 20 °С, and then the mixture was poured in a cold
water (200 mL). The organic layer was separated, washed with
water (2×50 mL), and dried with MgSO4. After the solvent was
distilled off in vacuo, the residue was chromatographed on Al2O3
using a hexane—СH2Cl2 (3 : 1) mixture as eluant. Comꢀ
pound 1 was obtained as orange crystals in 92% yield (5.8 g),
m.p. 182—183 °С (cf. Ref. 11: m.p. 181 °С (with decomp.)).
Found (%): С, 65.71; H, 4.09; Fe, 26.54. C23H18Fe2O. Calcuꢀ
lated (%): C, 65.58; H, 4.28; Fe, 26.36. IR, ν/cm–1: 729, 821,
850, 887, 1003, 1100, 1109, 1480, 1602, 1825, 1850, 2917, 3100.
1Н NMR, δ: 4.25 (s, 10 H, 2 C5H5); 4.58, 4.84 (both m, 4 H each,
C5H4). 13C NMR, δ: 65.16 (2 CipsoFc); 70.0 (2 C5H5); 70.9,
71.93 (2 C5H4); 144.9 (2 C); 152.3 (C=O).
Reaction of cyclopropenone 1 with EtMgCl. A 2 М solution
of EtMgCl in Et2O (8 mL, 16 mmol) was added dropwise to a
solution of compound 1 (0.84 g, 2 mmol) in anhydrous benzene
(100 mL). The mixture was stirred for 3 h at 20 °C, and then
water (100 mL) was added. The organic layer was separated and
washed with water, and benzene was distilled off in vacuo. The
residue was chromatographed on a column with Al2O3 using a
hexane—diethyl ether (3 : 1) mixture as eluant. Products 2—5
were isolated.
been described previously for the reactions of ferrocenyl
ketones with alkylmagnesium iodides.16,17
Diferrocenyl ketones 3, 4а,b, 7, and 8а,b were eviꢀ
dently formed due to the small ring closure in 11а,b
followed by the transformation into diferrocenylvinyl
carbenoid intermediates 12а,b. The latter add the second
RMgCl molecule and are transformed into vinyl anions
13а,b (Scheme 5).
The intramolecular alkylation of the phenyl fragment
of carbenoid 14 affords enolate 15. The insertion of
carbenoid 12а,b at one of the σꢀbonds of the starting
cyclopropenone 1 affords enoxide 16а,b. The treatment
of the reaction mixture with water transforms intermediꢀ
ates 12а,b, 13а,b, and enolates 15 (with simultaneous
oxidation by air oxygen) and 16а,b into target compounds
3, 4a,b, 5, 7, 8a,b, 9, and 10.
The scheme proposed is favored by the isolation of
deuterated ketones 3ꢀD and 4а,bꢀD upon decomposition
of the reaction mixture of diferrocenylcyclopropenone
and EtMgCl with heavy water D2O (Scheme 6).
1,2ꢀDiferrocenylꢀ3,3ꢀdiethylcyclopropene (2), 22% yield
(0.20 g), orange crystals, m.p. 168—169 °C. Found (%): С, 69.74;
H, 6.21; Fe, 23.87. C27H28Fe2. Calculated (%): C, 69.86;
H, 6.08; Fe, 24.06. IR, ν/cm–1: 721, 824, 1004, 1120, 1267,
Scheme 6
1
1464, 1609, 1643, 2859, 2920, 3095. Н NMR, δ: 0.98 (t, 6 H,
2 Me, J = 7.5 Hz); 1.70 (q, 4 H, 2 CH2, J = 7.5 Hz); 4.15 (s,
10 H, 2 C5H5); 4.33, 4.46 (both m, 4 H each, C5H4). 13C NMR,
δ: 12.5 (2 Me); 29.5 (2 CH2); 32.2 (C); 68.6, 68.9 (2 C5H4); 69.3
(2 C5H5); 75.2 (2 CipsoFc); 117.0 (2 C). MS, m/z 464 [M]+.
cisꢀ1,2ꢀDiferrocenylpentꢀ1ꢀenꢀ3ꢀone (3), 5% yield (0.046 g),
red powder, m.p. 146—147 °C. Found (%): С, 66.69; H, 5.22;
Fe, 24.89. C25H24Fe2О. Calculated (%): C, 66.41; H, 5.35;
Fe, 24.70. IR, ν/cm–1: 812, 1009, 1110, 1276, 1484, 1641, 1668,
1723, 2859, 2920, 3095. 1Н NMR, δ: 1.21 (t, 3 H, Me, J =
7.0 Hz); 3.48 (q, 2 H, CH2, J = 7.0 Hz); 4.11, 4.13, 4.23, 4.31,
4.37, 4.44 (all m, 2 H each, C5H4); 6.72 (s, 1 H, CH=).
13C NMR, δ: 14.6 (CH3); 39.3 (CH2); 67.8, 69.9, 70.8, 71.0
(2 C5H4); 69.1, 69.7 (2 C5H5); 78.4, 78.7 (2 CipsoFc); 136.0 (C);
136.6 (CH=); 198.4 (C=O). MS, m/z 453 [M]+.
The deuterium content in position 4 of saturated
ketone 4а,bꢀD decreased, most probably, due to isoꢀ
tope exchange during chromatography on a column
with Al2O3.
4,5ꢀDiferrocenylheptanꢀ3ꢀone (4), 50% yield (0.45 g), orꢀ
ange oil, a mixture of two isomers 4а and 4b in a ratio of ~3 : 1
(according to the data of Н NMR spectroscopy). The isomers
Experimental
1
Solvents were dried by standard procedures and distilled
before use. Fixedꢀbed SiO2 plates and Al2O3 (activity grade III
according to Brockmann) were used for chromatography. 1Н and
13С NMR spectra were recorded on a Varian Unity Inova specꢀ
trometer (300 and 75 MHz, respectively) for solutions in CDCl3
using Me4Si as internal standard.
IR spectra were recorded on a Specord IRꢀ75 spectrometer
(KBr pellets). Molecular weights were determined on a Varianꢀ
MAT CHꢀ6 mass spectrometer (EI, 70 eV) .
The following reagents available from Aldrich were used:
ferrocene, 98%; tetrachlorocyclopropene, 98%; aluminum chloꢀ
ride 99.99%; ethylmagnesium chloride, 2.0 М solution in Et2O;
and benzylmagnesium chloride, 1.0 М solution in Et2O.
2,3ꢀDiferrocenylcyclopropenone (1). AlCl3 (0.67 g,
0.005 mol) was added by portions with stirring to a solution of
were separated by TLC on fixedꢀbed SiO2 plates (hexane—diꢀ
ethyl ether (4 : 1)).
Compound 4а, 30% yield (0.27 g), Rf 0.68, orange crystals,
m.p. 176—177 °C. Found (%): С, 67.41; H, 6.09; Fe, 23.31.
C27H30Fe2O. Calculated (%): C, 67.25; H, 6.27; Fe, 23.16. IR,
ν/cm–1: 762, 815, 998, 1102, 1145, 1250, 1435, 1520, 1709,
2931, 3089. 1Н NMR, δ: 0.75 (t, 3 H, Me, J = 7.5 Hz): 0.92 (t,
3 H, Me, J = 7.2 Hz); 1.80 (m, 2 H, CH2); 2.41 (q, 2 H, CH2,
J = 7.2 Hz); 2.46 (m, 1 H, CH); 3.22 (d, 1 H, СН, J = 9.0 Hz);
3.85 (m, 1 H, C5H4); 3.92 (m, 2 H, C5H4); 3.99 (s, 5 H, C5H5);
4.02 (m, 1 H, C5H4); 4.06 (s, 5 H, C5H5); 4.09 (m, 2 H, C5H4);
4.16, 4.36 (both m, 1 H each, C5H4). 13C NMR, δ: 6.9, 12.5
(2 Me); 26.5, 38.3 (2 CH2); 46.0, 58.4 (2 CH); 66.3, 66.6, 66.9,
67.5, 68.3, 68.6, 69.3, 69.7 (2 C5H4); 68.4, 68.4 (2 C5H5); 84.1,
93.5 (2 CipsoFc); 210.95 (C=O). MS, m/z 482 [M]+.

840
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
Klimova et al.
Compound 4b, 10% yield, (0.10 g), orange powder, m.p.
3,3ꢀDibenzylꢀ1,2ꢀdiferrocenylcyclopropene (6), 20% yield
(0.24 g), orange crystals, m.p. 112—113 °C. Found (%): С, 75.39;
H, 5.67; Fe, 19.20. C37H32Fe2. Calculated (%): C, 75.53;
H, 5.48; Fe, 18.99. IR, ν/cm–1: 718, 821, 1003, 1105, 1258,
164—165 °C. IR, ν/cm–1: 768, 824, 1004, 1100, 1125, 1231,
1425, 1512, 1689, 2919, 3086. 1Н NMR, δ: 0.94 (t, 3 H, Me, J =
7.3 Hz); 1.05 (t, 3 H, Me, J = 7.5 Hz); 1.88 (m, 2 H, CH2); 2.45
(q, 2 H, CH2, J = 7.5 Hz); 2.49 (m, 1 H, CH); 3.56 (d, 1 H, CH,
J = 5.1 Hz); 3.67, 3.76, 3.79, 3.94 (all m, 1 H each, C5H4); 3.97,
4.04 (both s, 5 H each, C5H5); 4.03, 4.08 (both, 2 H each,
C5H4). 13C NMR, δ: 8.4, 13.6 (2 Me); 24.7, 37.3 (2 CH2); 46.1,
56.6 (2 CH); 66.7, 67.0, 68.0, 68.7 (2 C); 68.9, 69.6, 69.7
(2 C5H4); 68.4, 68.5 (2 C5H5); 91.3, 94.0 (2 CipsoFc); 210.1
(C=O). MS, m/z 482 [M]+.
1
1470, 1589, 1623, 1645, 2883, 2936, 3085. Н NMR, δ: 2.96 (s,
4 H, 2 CH2); 4.10 (s, 10 H, 2 C5H5); 4.33, 4.39 (both m,
4 H each, C5H4); 7.15—7.29 (m, 10 H, 2 C6H5). 13C NMR, δ:
33.3 (C); 43.9 (2 CH2); 68.9, 69.0 (2 C5H4); 69.3 (2 C5H5); 74.4
(2 CipsoFc); 117.7 (2 C); 125.7, 127.9, 129.9 (2 C6H5); 140.9
(2 Cipso). MS, m/z 588 [M]+.
cisꢀ4ꢀPhenylꢀ1,2ꢀdiferrocenylbutꢀ1ꢀenꢀ3ꢀone (7), 6% yield
(0.077 g), red powder, m.p. 161—162 °C. Found (%): С, 69.88;
H, 5.28; Fe, 21.93. C30H26Fe2О. Calculated (%): C, 70.07;
H, 5.10; Fe, 21.72. IR, ν/cm–1: 815, 1003, 1106, 1265, 1467,
4ꢀ(1ꢀFerrocenylꢀ2ꢀoxobutyl)ꢀ2,3,4ꢀtriferrocenylcycloꢀ
butenone (5), 6% yield (6%), violet powder, m.p. 289—292 °С
(with decomp.). Found (%): С, 66.19; H, 4.71; Fe, 25.77.
C48H42Fe4O2. Calculated (%): C, 65.94; H, 4.84; Fe, 25.56.
1Н NMR (δ: 1.28 (t, 3 H, Me, J = 7.2 Hz); 2.92 (q, 2 H, CH2,
J = 7.2 Hz); 3.48 (s, 1 H, CH); 3.92, 3.96 (both m, 1 H each,
C5H4); 4.06 (s, 5 H, C5H5); 4.10 (m, 2 H, C5H4); 4.11, 4.18,
4.23 (all s, 5 H each, C5H5); 4.25, 4.36, 4.41, 4.41 (all m,
2 H each, C5H4); 4.46 (m, 1 H, C5H4); 4.51 (m, 2 H, C5H4);
4.91 (m, 1 H, C5H4). 13C NMR, δ: 16.5 (CH3); 48.0 (CH2); 58.9
(CH); 66.9, 67.4, 67.4 (2 С); 67.5, 68.4, 68.6, 68.9 (2 С); 69.1,
69.2, 69.5, 70.5, 70.6, 70.9, 71.5 (4 C5H4); 69.0, 69.2, 69.4, 69.9
(4 C5H5); 73.0, 73.3, 80.3, 89.7 (4 CipsoFc); 140.1, 167.0, 185.7
(3 С); 198.9, 206.2 (2 C=O). MS, m/z 874 [M]+.
Decomposition of the reaction mixture with D2O. The reacꢀ
tion was carried out similarly to the procedure described above,
and D2O (100 mL) was added to decompose the reaction mixꢀ
ture. Compounds 2—5 were obtained after chromatography on
a column with Al2O3, hexane—diethyl ether (3 : 1) mixture as
eluant).
Cyclopropene 2, 20% yield, 0.18 g, orange crystals,
m.p. 169 °C.
Compound 3ꢀD, 5.5% yield (0.05 g), red powder, m.p.
146 °C. 1Н NMR, δ: 1.20 (t, 3 H, Me, J = 7.0 Hz); 3.46 (q, 2 H,
CH2, J = 7.0 Hz); 4.10, 4.13 (both s, 5 H each, C5H5); 4.24,
4.32, 4.38, 4.43 (all m, 2 H each, C5H4); 6.72 (s, 0.16 H, CH=).
MS, m/z 454 [M]+.
Compounds 4а,bꢀD, 56% yield (0.51 g), orange oil, mixture
of isomers 4аꢀD and 4bꢀD in a ratio of ~3 : 1 (according to the
data of 1Н NMR spectroscopy). MS, m/z: 483, 484 [M]+.
Compound 4аꢀD. 1Н NMR, δ: 0.76 (t, 3 H, Me, J = 7.3 Hz);
0.92 (t, 3 H, Me, J = 7.2 Hz); 1.81 (q, 2 H, CH2, J = 7.3 Hz);
2.41 (q, 2 H, CH2, J = 7.2 Hz); 2.46 (m, 0.13 H, CH); 3.22 (s,
0.6 H, СН); 3.85 (m, 1 H, C5H4); 3.92 (m, 2 H, C5H4); 3.99 (s,
5 H, C5H5); 4.02 (m, 1 H, C5H4); 4.06 (s, 5 H, C5H5); 4.09 (m,
2 H, C5H4); 4.16, 4.36 (both m, 1 H each, C5H4).
Compound 4bꢀD. 1Н NMR, δ: 0.95 (t, 3 H, Me, J = 7.2 Hz);
1.04 (t, 3 H, Me, J = 7.5 Hz); 1.89 (q, 2 H, CH2, J = 7.2 Hz);
2.44 (q, 2 H, CH2, J = 7.5 Hz); 2.49 (m, 0.12 H, CH); 3.56 (s,
0.55 H, CH); 3.67, 3.76, 3.79, 3.94 (all m, 1 H each, C5H4);
3.97 (s, 5 H, C5H5); 4.03 (m, 2 H, C5H4); 4.04 (s, 5 H, C5H5);
4.07 (m, 2 H, C5H4).
1
1620, 1648, 1665, 1715, 2853, 2918, 3095. Н NMR, δ: 3.01 (s,
2 H, CH2); 4.08, 4.15 (both s, 5 H each, C5H5); 4.28, 4.33, 4.37,
4.49 (all m, 2 H each, C5H4); 6.86 (s, 1 H, CH=). 13C NMR, δ:
42.3 (CH2); 67.8, 68.8, 70.5, 70.6 (2 C5H4); 69.3, 69.7 (2 C5H5);
81.2, 82.6 (2 CipsoFc); 126.5, 128.5, 130.9 (C6H5); 137.2 (C);
138.2 (CH=); 140.6 (Cipso); 199.1 (C=O). MS, m/z 514 [M]+.
1,5ꢀDiphenylꢀ3,4ꢀdiferrocenylpentꢀ3ꢀenꢀ2ꢀone (8), 45% yield
(0.54 g), orange powder, m.p. 183—188 °C, mixture of two
diastereomers 8а and 8b in a ratio of ~3 : 1 (data of the 1H NMR
spectroscopy). Found (%): С, 73.41; H, 5.39; Fe, 18.31.
C37H34Fe2O. Calculated (%): C, 73.29; H, 5.65; Fe, 18.42. IR,
ν/cm–1: 767, 823, 1021, 1110, 1233, 1448, 1525, 1536, 1654,
1710, 2921, 3098. MS, m/z 606 [M]+.
1
Compound 8a. Н NMR, δ: 2.61 (m, 1 H, CH); 3.15 (d,
2 H, CH2, J = 6.3 Hz); 3.23 (s, 2 H, CH2), 3.54 (d, 1 H, CH, J =
8.4 Hz); 4.05 (m, 1 H, C5H4); 4.09 (s, 5 H, C5H5); 4.12 (m, 2 H,
C5H4); 4.14 (s, 5 H, C5H5); 4.15 (m, 1 H, C5H4); 4.18 (m, 2 H,
C5H4); 4.21, 4.46 (both m, 1 H each, C5H4); 6.89—7.54 (m,
10 H, 2 C6H5).
1
Compound 8b. Н NMR, δ: 2.68 (m, 1 H, CH); 3.10 (d,
2 H, CH2, J = 6.6 Hz); 3.30 (s, 2 H, CH2); 3.41 (d, 1 H, CH, J =
8.7 Hz); 3.95 (m, 1 H, C5H4); 4.00 (s, 5 H, C5H5); 4.02 (m, 2 H,
C5H4); 4.10 (s, 5 H, C5H5); 4.13 (m, 1 H, C5H4); 4.15 (m, 2 H,
C5H4); 4.17, 4.32 (both m, 1 H each, C5H4); 7.04—7.63 (m,
10 H, 2 C6H5).
4ꢀ(3ꢀPhenylꢀ1ꢀferrocenylꢀ2ꢀoxopropyl)ꢀ2,3,4ꢀtriferrocenylꢀ
cyclobutenone (9), 6% yield (0.053 g), violet powder, m.p.
312—315 °С (with decomp.). Found (%): С, 68.21; H, 4.91;
Fe, 23.65. C53H44Fe4O2. Calculated (%): C, 67.98; H, 4.74;
1
Fe, 23.86. Н NMR, δ: 3.23 (s, 2 H, CH2); 3.52 (s, 1 H, CH);
4.02, 4.07 (both m, 1 H each, C5H4); 4.09 (s, 5 H, C5H5); 4.13
(m, 2 H, C5H4); 4.14, 4.26 (both s, 5 H each, C5H5); 4.29 (m,
2 H, C5H4); 4.39 (s, 5 H, C5H5); 4.40, 4.52, 4.54 (all m, 2 H each,
C5H4); 4.56 (m, 1 H, C5H4); 4.61 (m, 2 H, C5H4); 4.99 (m, 1 H,
C5H4); 7.09—7.45 (m, 5 Н, C6H5). 13C NMR, δ: 47.4 (CH2);
57.7 (CH); 67.2, 67.4, 67.6 (2 С); 67.7, 68.7, 68.8, 69.0 (2 С);
69.2, 69.3, 69.6, 70.5, 70.6, 71.0, 71.6 (4 C5H4); 69.1, 69.2, 69.5,
69.9 (4 C5H5); 73.3, 73.5, 80.6, 89.9 (4 CipsoFc); 128.3, 129.5,
134.3 (C6H5); 139.2 (Cipso); 140.3, 159.9, 175.6 (3 С); 194.3,
209.1 (2 C=O). MS, m/z 936 [M]+.
2ꢀHydroxyꢀ3ꢀoxoꢀ1,2ꢀdiferrocenylꢀ1,2,3,4ꢀtetrahydroꢀ
naphthalene (10), 10% yield (0.10 g), orange powder, m.p.
159—160 °С Found (%): С, 67.78; H, 5.13; Fe, 21.29.
C30H26Fe2О2. Calculated (%): C, 67.95; H, 4.94; Fe, 21.06. IR,
ν/cm–1: 823, 1013, 1100, 1256, 1464, 1625, 1661, 1718, 2879,
2905, 3095, 3368—3459. 1Н NMR, δ: 3.14 (s, 2 H, CH2); 3. 63
(s, 1 Н, СН); 4.08 (s, 5 H, C5H5); 4.12 (m, 2 H, C5H4); 4.21 (s,
Compound 5, 5% yield (0.05 g), violet powder, m.p.
289—291 °С (with decomp.). MS, m/z 874 [M]+.
Reaction of cyclopropenone 1 with BnMgBr. Compounds
6—10 were synthesized similarly from compound 1 (0.84 g,
2 mmol) in anhydrous benzene (100 mL) and a 1 М solution of
BnMgCl in Et2O (16.0 mL) after the respective treatment and
chromatography on Al2O3 (hexane—diethyl ether (2 : 1) as
eluant).

2,3ꢀDiferrocenylcyclopropenone
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 4, April, 2004
841
5 H, C5H5); 4.23, 4.27, 4.34 (all m, 2 H each, C5H4); 5.03 (br.s,
1 Н, ОН); 6.98—7.35 (m, 4 H, C6H4). 13C NMR, δ: 41.1 (CH2);
67.5, 68.9, 70.4, 70.5 (2 C5H4); 69.3, 69.7 (2 C5H5); 70.2 (C);
78.9, 80.7 (2 CipsoFc); 127.8, 129.3, 129.8, 134.3 (C6H4); 136.5,
144.8 (2 Cipso); 210.1 (C=O). MS, m/z 530 [M]+.
4. R. Breslow, R. Haynie, and J. Mirra, J. Am. Chem. Soc.,
1959, 81, 247.
5. I. Agranat and S. Kohen, Bull. Chem. Soc. Jpn, 1974, 47, 723.
6. H. Tsukada, H. Shimanouchi, and Y. Sasada, Tetrahedron
Lett., 1973, 2455.
Xꢀray diffraction analysis of compounds 4а and 6. Unit cell
parameters and intensities of reflections were measured on a
Bruker Smart Apex CCD diffractometer at 291 K. The strucꢀ
tures were solved by the direct method and refined by the leastꢀ
squares method in the fullꢀmatrix anisotropic approximation for
nonꢀhydrogen atoms. All H atoms were revealed from the differꢀ
ence series and refined isotropically. The coordinates of atoms
were deposited with the Cambridge Structural Database. The
crystallographic data, parameters of Xꢀray diffraction experiꢀ
ment, and refinement parameters are presented in Table 2.
7. Y. VeprekꢀBilinski, K. Natasimhan, and A. S. Dreiding, Helv.
Chim. Acta, 1978, 61, 3018.
8. M. Takahashi, N. Inaba, H. Kirihara, and S. Watanabe,
Bull. Chem. Soc. Jpn, 1978, 51, 3312.
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10. M. Takahashi and S. Watanabe, Chem. Lett., 1979, 1213.
11. I. Agranat, E. AharonꢀShalom, A. J. Fry, R. L. Krieger, and
W. O. Krug, Tetrahedron, 1979, 35, 733.
12. E. I. Klimova, T. Klimova Berestneva, L. Ruiz Ramirez,
M. Martinez Garcia, C. Alvarez Toledano, P. G. Espinosa,
and R. A. Toscano, J. Organomet. Chem., 1997,
545—546, 191.
13. E. I. Klimova, M. Martinez Garcia, T. Klimova, C. Alvarez
Toledano, R. A. Toscano, R. Moreno Esparza, and L. Ruiz
Ramirez, J. Organomet. Chem., 1998, 566, 175.
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A. Cinquantini, M. Corsini, P. Zanello, S. Hernandez
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2003, 4265.
The authors thank O. S. Yañez Muñoz, M. L. Velasco,
J. Perez, H. Rios, and R. Patiño for measuring mass, IR,
and NMR spectra.
This work was financially supported by the Naꢀ
tional Council on Science and Technology (CONACyT
(Mexico), Grant 34862ꢀE).
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Received June 23, 2003;
in revised form October 20, 2003