Diferrocenyl(hydroxy)oxazepines and diferrocenyl-4-aza-1,3-dienes in the reactions of 2,3-diferrocenyl-1-methylthiocyclopropenylium iodide with aromatic and aliphatic bis-1,4-N,O-nucleophiles

Article abstract of DOI:10.1016/j.poly.2019.07.019

A novel method for the synthesis of 3,4-diferrocenyl-2-methylthio-2,3-dihydrobenzo[b]-1,4-oxazepin-3-ols 7a–e (23–30%), 3,4-diferrocenylquinolin-8-ols 8b–d (9–16%), 1-E-2,3-diferrocenyl-4-(2-hydroxyphenyl)-1-methylthio-4-aza-1,3-dienes 9a–e (24–30%), cis-

Full text of DOI:10.1016/j.poly.2019.07.019

Polyhedron 171 (2019) 353–364
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Diferrocenyl(hydroxy)oxazepines and diferrocenyl-4-aza-1,3-dienes in
the reactions of 2,3-diferrocenyl-1-methylthiocyclopropenylium iodide
with aromatic and aliphatic bis-1,4-N,O-nucleophiles
⇑
Jessica J. Sánchez García , Jose A. Castella-Lasaga, Marcos Flores-Álamo, José M. Méndez Stivalet,
Elena I. Klimova
⇑
Facultad de Química, Universidad Nacional Autónoma de México, Cd. Universitaria, Coyoacán, C.P. 04510 México, CDMX, Mexico
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel method for the synthesis of 3,4-diferrocenyl-2-methylthio-2,3-dihydrobenzo[b]-1,4-oxazepin-3-
ols 7a–e (23–30%), 3,4-diferrocenylquinolin-8-ols 8b–d (9–16%), 1-E-2,3-diferrocenyl-4-(2-hydrox-
Received 21 May 2019
Accepted 15 July 2019
Available online 27 July 2019
yphenyl)-1-methylthio-4-aza-1,3-dienes
9a–e
(24–30%),
cis-/trans-2,3-diferrocenyl-3-methylth-
ioacroleins 10a,b (7–19%), S,R-5,6-diferrocenyl-7-methylthio-2,3,6,7-tetrahydro-1,4-oxazepin-6-ols
13b,d,e (28–33%) and E,Z- and Z,E-2,3-diferrocenyl-6-hydroxy-1-methylthio-4-aza-1,3-alkadienes 14a–
e (29–34%) and 15a–e (10–13%) by reactions of 2,3-diferrocenyl-1-sulfanyl-cyclopropenylium iodide 2
with aromatic and aliphatic bis-1,4-N,O-nucleophiles (1,2-aminophenols 3a–e and 1,2-aminoalcohols
11a–e) in the presence of Et3N is presented. A new reaction for the transformation of the intermediate
products of the addition of bis-1,4-N,O-nucleophiles 3a–e and 11a–e to the diferrocenylcyclopropenilium
cation 2 in the positions C(1) and C(2) is found. The characterization of the new compounds was con-
ducted by IR, 1H and 13C NMR spectroscopy, mass-spectrometry, elemental analysis, and X-ray
diffraction.
Keywords:
Ferrocene
Biferrocenyl compounds
Ferrocenyl oxazepines
Cyclopropenilium
Diferrocenyl-butadienes
Ó 2019 Elsevier Ltd. All rights reserved.
1. Introduction
properties, e.g., thermal stability [8], magnetic behavior [9], elec-
tric conductivity (even superconductivity) [10], nonlinear optical
Bi- and polynuclear ferrocenyl compounds containing conju-
gated systems and functional groups in their molecules have
effects [11], bioactivity [12].
p
In the last two decades, diferrocenylcyclopropenylium salts
have been studied as possible initial compounds in the synthesis
of diferrocenyl-substituted organic compounds [13]. This method-
ology is based on the capacity of diferrocenylcyclopropenylium
cations for the opening of the three-carbon cycle in the reactions
with mono C-, N-, O-nucleophiles and di-N,N-, di-N,O-nucleophiles,
leading to the formation of polyene, carbo- and heterocyclic prod-
ucts with several ferrocene groups. The latter property makes it
possible to use these cations for introducing the 1,2-diferrocenyl-
propene fragment as a three-carbon building block into organic
compounds. In addition, the functional groups (OR, NR2, SR) at
the C(1) carbon atom of the three-membered cycle of diferrocenyl-
cyclopropenylium have been found to affect the regioselectivity of
the processes in the interactions with nucleophiles, which is
expressed in the nucleophilic attacks of the reagents predomi-
nantly on the carbon atom C(1) or C(2) and in subsequent transfor-
mations of the intermediates [14]. This phenomenon has been
insufficiently studied until now, although it is of interest for the
recently attracted much interest in organometallic chemistry [1].
This interest is due to the unique physicochemical properties of
these compounds [2], which make them promising components
for the synthesis of catalytic [3], photochemical, electrochemical
[4], pharmacological [5], and other systems on their basis. The syn-
thesis of many organic compounds of the ferrocene series is based
on a fairly high availability of functionalized ferrocene derivatives
[6], such as ferrocenyl carbaldehyde, acetylferrocene, ferrocenyl-
lithium, diaminomethylferrocene, a,b-enones with ferrocenyl sub-
stituents in their molecules [7]. On the basis of these initial
compounds, different methods of synthesis have been developed
for many polyene, carbo- and heterocyclic products with ferrocene
groups in their molecules. These products have various useful
⇑
Corresponding authors. Fax: +52 555622 5371.
E-mail address: heparina250ml@ciencias.unam.mx (E.I. Klimova).
https://doi.org/10.1016/j.poly.2019.07.019
0277-5387/Ó 2019 Elsevier Ltd. All rights reserved.

354
J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
synthesis of polyferrocenyl-substituted organic compounds of var-
ious classes that cannot be obtained using other methods [15].
It is already known that much attention is paid to the synthesis
of novel derivatives of mono- and polycyclic heterocycles contain-
ing several heteroatoms in a cycle, since such heterocycles are
often present as important structural elements in many natural
and medicinal compounds. Ferrocenyl-substituted heterocycles of
these types are of special interest in the search for bioactive sub-
stances. These compounds include ferrocenyl derivatives of pyra-
zolines [16], pyrazoles [17], thiazoles [18], oxazoles [19],
quinuclidines [20], pyrimidines [21], triazines [22], imidazole
[23], etc.
This study investigates the interaction of bis-1,4-N,O-nucle-
ophiles of the aliphatic and aromatic series with 2,3-diferrocenyl-
1-methylthiocyclopropenylium iodide with the aim of developing
a novel method for the synthesis of hydroxyl-1,3-diene systems
and heterocyclic products, like 1,4-oxazines or 1,4-oxazepines.
2.3. Reaction of 2,3-diferrocenyl-1-methylthiocyclopropenylium iodide
(2) with 1,2-aminophenols (3a–e) or 1,2-aminoalcohols (11a–e)
(general procedure)
1,2-Aminophenol 3a [or 3b–e, or 1,2-aminoalcohols 11a–e]
(2.5 mmol) and Et3N (1.0 mL) was added to a stirring solution of
2,3-diferrocenyl-1-methylthiocyclopropenylium iodide 2 (3.0 mmol)
in dry benzene (70 mL) under a nitrogen atmosphere. The reaction
mixture was heated to refluxing conditions (6–8 h), the solvent
was removed in vacuo and the residue was dissolved in dichloro-
methane (30 mL). The solution was mixed with (Al2O3, Brockmann
activity III) (20 g) and the solvent was evaporated in air. This mate-
rial was placed on the top of a column with Al2O3 (the height of
alumina is ca. 20 cm) and the elution was performed first with hex-
ane and then with hexane–ether (3:1), hexane–dichloromethane
(4:1) to afford compounds 4, 5a, 6a, 7a, 9a, 10a,b [or (4, 5b–e,
6b–e, 7b–e, 8b–d, 9b–e, 10a,b), or (4, 12a–e, 13b-e, 14a–e
+ 15a–e, 10a,b)]. cis-14a–e and trans-15a–e isomers were isolated
by thin-layer chromatography (TLC) on Al2O3 or silica in a solvent
system hexane–ether (4:1). The physicochemical characteristics of
compounds 4, 5a–e, 6a–e, 8c,d and 12a–e were in accordance with
the literature data (See Supplementary material) [27–29].
2. Experimental
2.1. Materials and physical measurements
2.3.1. S,R-3,4-Diferrocenyl-2-methylthio-2,3-dihydrobenzo[b]-1,4-
oxazepin-3-ol (7a)
Orange powder, yield 0.370 g (26%), m.p. 158–160 °C. IR (KBr):
810, 825, 1001, 1102, 1179, 1244, 1285, 1342, 1422, 1431, 1457,
All the solvents were dried according to the standard proce-
dures and freshly distilled before use. Column chromatography
was carried out on alumina (Brockmann activity III). The 1H and
13C NMR spectra were recorded on a Unity Inova Varian spectrom-
eter (400-MHz and 100 MHz) for solutions in CDCl3 with Me4Si as
the internal standard. Chemical shifts (d, ppm) were reported with
respect to residual solvent peaks as internal standard (1H: CDCl3,
d = 7.26 ppm, 13C: CDCl3, d = 77.2 ppm), d values were measured
with precision 0.01 ppm. The IR spectra were measured on a Spec-
trophotometer FT-IR (Spectrum RXI Perkin Elmer 400 instruments)
using KBr pellets. The mass spectra were obtained on a Varian MAT
CH-6 instrument (EI MS, 70 eV). An Elementar Analysensysteme
LECO CHNS-900 was used for elemental analyses.
The following reagents were purchased from Aldrich: ferrocene,
98%; aluminum chloride, 99.99%; tetrachlorocyclopropene, 98%;
Lawesson reagent, 97%; triethylamine, 99.5%; iodomethane,
99.5%; 2-aminophenol, 99%; 2-amino-4-methylphenol, 97%; 2-
amino-4-tert-butylphenol, 98%; 2-amino-4-chlorophenol, 97%;
2-amino-4-nitrophenol, 96%; ethanolamine, 99.5+%; 2-amino-
2-phenylethanol, 98%; 2-amino-3-phenylpropanol, 98%; 2-amino-
1-phenylethanol, 98%; 2-amino-3-methyl-1-butanol, 97%.
The starting material 2,3-diferrocenylcyclopropenone was
obtained from the ferrocene and tetrachlorocyclopropene in the
presence of AlCl3. 2,3-Diferrocenyl-1-methylthiocyclopropenylium
iodide 2 was obtained from 2,3-diferrocenylcyclopropenthione 1
and methyl iodide according to the standard procedures [24–27],
respectively. The physical and 1H NMR spectroscopic characteris-
tics of 2,3-diferrocenylcyclopropenone and 2,3-diferrocenyl-1-
methylthiocyclopropenylium iodide 2 were in accord with the lit-
erature data [24].
m
1492, 1589, 1600, 1658, 2867, 2883, 2946, 2986, 3098, 3176,
3430 cmÀ1 1H NMR (400 MHz, CDCl3): d 2.03 (3H, s, CH3), 3.87
.
(1H, bs, OH), 4.02 (5H, s, C5H5), 4.28 (5H, s, C5H5), 4.12, 4.14,
4.16, 4.24, 4.32, 4.67, 4.90, 5.01 (2C5H4), 5.43 (1H, s, CH), 7.35
(2H, bs, C6H4), 7.41 (2H, bs, C6H4). 13C NMR (100 MHz, CDCl3): d
14.05 (CH3), 68.94, 69.99 (2C5H5), 67.22, 67.81, 68.12, 68.25,
69.35, 70.33, 70.80, 71.20 (2C5H4), 79.76, 84.20 (2CipsoFc), 91.02
(CH), 128.77, 130.87 (C6H4), 92.17, 127.93, 134.13, 167.76 (4C).
Anal. Calc. for C30H27Fe2NO2S (577.22): C, 62.42; H, 4.72; N, 2.43;
S, 5.54. Found: C, 62.50; H, 4.79; N, 2.42, S, 5.52%. MS (El, 70 eV):
m/z 577 [M]+.
2.3.2. S,R-3,4-Diferrocenyl-7-methyl-2-methylthio-2,3-dihydrobenzo
[b]-1,4-oxazepin-3-ol (7b)
Orange powder, yield 0.440 g (30%), m.p. 157–158 °C. IR (KBr):
806, 821, 930, 999, 1027, 1104, 1249, 1296, 1323, 1351, 1404,
m
1457, 1498, 1572, 1594, 1616, 2842, 2941, 2980, 3088, 3188,
3437 cmÀ1 1H NMR (400 MHz, CDCl3): d 2.28 (3H, s, CH3), 2.36
.
(3H, s, CH3), 3.99 (1H, s, OH), 4.12 (5H, s, C5H5), 4.26 (5H, s,
C5H5), 3.86, 4.08, 4.17, 4.23, 4.38, 4.42, 5.10, 5.13 (2C5H4), 5.46
(1H, s, CH), 6.90 (1H, d, J = 6.0 Hz, C6H3), 7.02 (1H, d, J = 6.0 Hz,
C6H3), 7.45 (1H, s, C6H3). 13C NMR (100 MHz, CDCl3): d 14.87,
20.32 (2CH3), 68.91, 69.84 (2C5H5), 65.53, 66.97, 67.70, 68.82,
69.75, 70.30, 70.55, 70.65 (2C5H4), 79.62, 83.73 (2CipsoFc), 90.93
(CH), 120.16, 129.28, 135.32 (C6H3), 92.51, 132.10, 135.39,
143.53, 167.22 (5C). Anal. Calc. for C31H29Fe2NO2S (591.24): C,
62.97; H, 4.94; N, 2.37; S, 5.41. Found: C, 62.77; H, 4.78; N, 2.42,
S, 5.50%. MS (El, 70 eV): m/z 592 [M]+.
2.2. Synthesis
2.3.3. S,R-7-Chloro-3,4-diferrocenyl-2-methylthio-2,3-dihydrobenzo
2.2.1. Synthesis of the 2,3-diferrocenylcyclopropenthione (1)
[b]-1,4-oxazepin-3-ol (7c)
A
mixture of the 2,3-diferrocenylcyclopropenone 3.4 g
Orange powder, yield 0.380 g (25%), m.p. 178–179 °C. IR (KBr):
802, 827, 1000, 1103, 1245, 1261, 1388, 1445, 1479, 1551, 1604,
1616, 2864, 2924, 2958, 3094, 3447 cmÀ1 1H NMR (400 MHz,
CDCl3): d 2.28 (3H, s, CH3), 3.80 (1H, bs, OH), 4.10 (5H, s, C5H5),
4.25 (5H, s, C5H5), 3.82, 3.95, 4.16, 4.22, 4.41, 4.45, 5.11, 5.16
(2C5H4), 5.45 (1H, s, CH), 7.13 (1H, bs, C6H3), 7.53 (1H, bs, C6H3),
7.70 (1H, s, C6H3). 13C NMR (100 MHz, CDCl3): d 14.06 (CH3),
68.93, 69.97 (2C5H5), 67.22, 68.13, 69.38, 70.33 (2C5H4), 79.76,
m
(8 mmol), Lawesson reagent 3.0 g (8.2 mmol) in 15 mL of the dry
benzene was heated to refluxed (80 °C) in an argon atmosphere
ꢀ6–8 h. The organic layer was concentrated, and the residue was
chromatographed on alumina (Brockmann activity III, hexane–
dichloromethane, 1:1) to give 2,3-diferrocenylcyclopropenthione
1, yield 3.15 g (7 mmol), 92%, m.p. 208–209 °C. (Lit. [24] m.p.
208–209 °C.)
.

J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
355
83.01 (2CipsoFc), 91.01 (CH), 128.77, 130.87, 134.14 (C6H3), 92.17,
127.93, 132.25, 144.54, 167.78 (5C). Anal. Calc. for C30H26 ClFe2-
NO2S (611.70): C, 58.90; H, 4.30; N, 2.20; S, 5.23. Found: C,
59.10; H, 4.50; N, 2.35, S, 5.48%. MS (El, 70 eV): m/z 612 [M]+.
(561.28): C, 64.19; H, 4.85; N, 2.49; S, 5.71. Found: C, 64.10; H,
4.52; N, 2.40; S, 5.52%. MS (El, 70 eV): m/z 561 [M]+
2.3.8. E,Z-2,3-Diferrocenyl-4-(2-hydroxy-5-methylphenyl)-1-
methylthio-4-aza-1,3-butadiene (9b)
2.3.4. S,R-3,4-Diferrocenyl-7-nitro-2-methylthio-2,3-dihydrobenzo
Orange powder, yield 0.390 g (27%), m.p. 152–154 °C. IR (KBr): m
[b]-1,4-oxazepin-3-ol (7d)
465, 480, 539, 642, 759, 806, 821, 868, 899, 953, 999, 1027, 1041,
Orange powder, yield 0.360 g (23%), m.p. 172–173 °C. IR (KBr):
814, 868, 1001, 1106, 1253, 1272, 1296, 1357, 1377, 1421, 1457,
1627, 2852, 2893, 2933, 2958, 3092, 3452 cmÀ1 1H NMR
(400 MHz, CDCl3): d 2.31 (3H, s, CH3), 3.79 (1H, s, OH), 4.08 (5H,
s, C5H5), 4.28 (5H, s, C5H5), 4.01, 4.02, 4.06, 4.13, 4.46, 4.51, 5.18,
5.21 (2C5H4), 5.50 (1H, s, CH), 7.03 (1H, d, J = 6.6 Hz, C6H3), 8.03
(1H, dd, J = 2.1, 6.6 Hz, C6H3), 8.51 (1H, d, J = 2.1 Hz, C6H3). 13C
NMR (100 MHz, CDCl3): d 15.12 (CH3), 68.99, 70.15 (2C5H5),
64.77, 67.51, 67.96, 69.09, 70.37, 70.60, 70.87, 71.91 (2C5H4),
79.91, 82.97 (2CipsoFc), 91.81 (CH), 121.09, 122.84, 130.63 (C6H3),
m
1084, 1104, 1162, 1187, 1249, 1296, 1350, 1403, 1456, 1498, 1572,
1594, 1615, 1736, 2785, 2842, 2874, 2941, 2980, 3088, 3435 cmÀ1
.
.
1H NMR (400 MHz, CDCl3): d 2.48 (3H, s, CH3), 2.53 (3H, s, CH3),
4.17 (5H, s, C5H5), 4.23 (5H, s, C5H5), 4.50, 4.77, 5.07, 5.55 (2C5
H4), 7.47 (1H, s, HC@), 7.35 (2H, m, C6H3), 7.58 (1H, d, J = 6.3 Hz,
C6H3), 7.71 (1H, s, OH). 13C NMR (100 MHz, CDCl3): d 21.51,
30.15 (2CH3), 69.82, 70.55 (2C5H5), 69.37, 70.12, 70.91, 71.98
(2C5H4), 79.23, 80.06 (2CipsoFc), 119.06, 125.11, 129.17 (C6H3),
135.45, (HC@), 121.66, 134.07, 142.45, 148.66, 166.32 (5C). Anal.
Calc. for C31H29Fe2NOS (575.24): C, 64.72; H, 5.08; N, 2.43; S,
5.56. Found: C, 64.70; H, 5.15; N, 2.40; S, 5.40%. MS (El, 70 eV):
m/z 575 [M]+.
91.65, 128.76, 135.69, 151.34, 171.66 (5C). Anal. Calc. for C30H26
-
Fe2N2O4S (622.21): C, 57.91; H, 4.21; N, 4.50; S, 5.14. Found: C,
57.80; H, 4.28; N, 4.50, S, 5.35%. MS (El, 70 eV): m/z 622 [M]+.
2.3.9. E,Z-2,3-Diferrocenyl-4-(2-hydroxy-5-chlorophenyl)-1-
2.3.5. S,R-7-tert-Butyl-3,4-diferrocenyl-2-methylthio-2,3-
methylthio-4-aza-1,3-butadiene (9c)
dihydrobenzo[b]-1,4-oxazepin-3-ol (7e)
Orange powder, yield 0.360 g (24%), m.p. 165–167 °C. IR (KBr): m
Orange powder, yield 0.400 g (25%), m.p. 168–169 °C. IR (KBr):
814, 833, 1000, 1107, 1116, 1258, 1276, 1317, 1385, 1412, 448,
1499, 1651, 2918, 3091, 3395, 3412 cmÀ1 1H NMR (400 MHz,
m
465, 480, 541, 642, 743, 764, 806, 821, 868, 900, 930, 954, 999,
1027, 1041, 1083, 1104, 1163, 1187, 1249, 1296, 1323, 1351,
1404, 1457, 1498, 1572, 1594, 1616, 2785, 2842, 2875, 2921,
.
CDCl3): d 1.35 (9H, s, 3CH3), 2.30 (3H, s, CH3), 4.03 (1H, s, OH),
4.15 (5H, s, C5H5), 4.29 (5H, s, C5H5), 3.95, 4.05, 4.07, 4.14, 4.24,
4.38, 4.40, 5.11 (2C5H4), 5.50 (1H, s, CH), 6.95 (1H, d, J = 6.0 Hz,
C6H3), 7.25 (1H, d, J = 6.0 Hz, C6H3), 7.85 (1H, s, C6H3). 13C NMR
(100 MHz, CDCl3): d 14.88 (CH3), 31.43 (3CH3), 68.92, 69.79
(2C5H5), 65.86, 66.82, 67.61, 68.82, 69.78, 69.84, 70.41, 70.83
(2C5H4), 79.58, 83.74 (2CipsoFc), 91.05 (CH), 119.75, 125.90,
131.95 (C6H3), 34.03, 92.62, 135.00, 143.47, 145.35, 166.86 (6C).
Anal. Calc. for C34H35Fe2NO2S (633.32): C, 64.48; H, 5.57; N, 2.21;
S, 5.06. Found: C, 64.37; H, 5.40; N, 2.32 %, S, 5.08. MS (El,
70 eV): m/z 633 [M]+.
2941, 2980, 3088, 3100, 3188, 3437 cmÀ1 1H NMR (400 MHz,
.
CDCl3): d 2.27 (3H, s, CH3), 4.10 (5H, s, C5H5), 4.25 (5H, s, C5H5),
3.82, 4.07, 4.45, 5.16 (2C5 H4), 7.14 (1H, s, HC@), 6.92 (1H, s,
C6H3), 7.53 (1H, bs, C6H3), 7.70 (1H, bs, C6H3), 8.09 (1H, bs, OH).
13C NMR (100 MHz, CDCl3): d 23.70 (CH3), 68.84, 69.99 (2C5H5),
65.19, 67.22, 67.81, 68.12, 70.04, 70.57, 70.67, 71.20 (2C5H4),
79.76, 83.96 (2CipsoFc), 135.45 (HC@), 128.77, 130.87, 134.17 (C6
H3), 125.37, 125.67, 132.36, 144.54, 167.76 (5C). Anal. Calc. for C30
-
H
26ClFe2NOS (595.66): C, 60.50; H, 4.40; N, 2.35; S, 5.37. Found: C,
60.62; H, 4.62; N, 2.45; S, 5.49%. MS (El, 70 eV): m/z 596 [M]+.
2.3.10. E,Z-2,3-Diferrocenyl-4-(2-hydroxy-5-nitrophenyl)-1-
methylthio-4-aza-1,3-butadiene (9d)
2.3.6. 3,4-Diferrocenyl-5-methylquinolin-8-ol (8b)
Orange powder, yield 0.400 g (25%), m.p. 168–169 °C. IR (KBr):
m
Orange powder, yield 0.390 g (26%), m.p. 160–162 °C. IR (KBr):
m
480, 806, 821, 999, 1027, 1041, 1104, 1162, 1249, 1295, 1350,
480, 642, 764, 806, 821, 868, 930, 999, 1027, 1041, 1083, 1104,
1163, 1187, 1249, 1296, 1323, 1351, 1404, 1457, 1498, 1572,
1594, 1616, 2842, 2921, 2941, 2980, 3088, 3100, 3188,
1404, 1456, 1498, 1572, 1594, 2785, 2941, 2980, 3058,
3435 cmÀ1 1H NMR (400 MHz, CDCl3): d 2.32 (3H, s, CH3), 4.02
.
(1H, s, OH), 4.14 (5H, s, C5H5), 4.28 (5H, s, C5H5), 3.95, 4.07, 4.14,
4.24, 4.38, 4.60, 4.80, 5.11 (C5H4), 5.50 (1H, s, CH), 6.95 (1H, d,
J = 6.0 Hz, C6H3), 7.25 (1H, d, J = 6.0 Hz, C6H3), 7.85 (1H, s, C6H3).
13C NMR (100 MHz, CDCl3): d 14.91 (CH3), 31.43 (3CH3), 68.92,
69.79 (2C5H5), 65.86, 66.82, 67.61, 68.82, 69.78, 69.84, 70.41,
70.83 (2C5H4), 79.58, 83.74 (2CipsoFc), 91.05 (CH), 119.75, 125.90,
131.95 (C6H3), 34.03, 92.62 135.00, 143.47, 145.35, 166.86 (6C).
Anal. Calc. for C34H35Fe2NO2S (633.32): C, 64.48; H, 5.57; N, 2.21;
S, 5.06. Found: C, 61.99; H, 4.50; N, 11.46%. MS (El, 70 eV): m/z
633 [M]+.
3437 cmÀ1 1H NMR (400 MHz, CDCl3): d 2.41 (3H, s, CH3), 4.04
.
(5H, s, C5H5), 4.17 (5H, s, C5H5), 4.27, 4.35, 4.50, 4.95 (2C5 H4),
7.36 (2H, m, C6H3), 7.41 (1H, s, C6H3), 7.88 (1H, s, HC@), 8.12
(1H, bs, OH). 13C NMR (100 MHz, CDCl3): d 18.70 (CH3), 68.92,
70.01 (2C5H5), 69.82, 70.01, 70.34, 71.20 (2C5 H4), 79.96, 82.54
(2CipsoFc), 91.02 135.58 (HC@), 128.61, 131.73, 134.01 (C6H3),
125.24, 125.45, 132.61, 144.49, 167.81 (5C). Anal. Calc. for C30H26
-
Fe2N2O3S (606.21): C, 59.44; H, 4.32; N, 4.62; S, 5.28. Found: C,
61.99; H, 4.50; N, 11.46%. MS (El, 70 eV): m/z 606 [M]+.
2.3.11. E,Z-7-4-(2-Hydroxy-5-tert-butylphenyl)-2,3-diferrocenyl-1-
2.3.7. E,Z-2,3-Diferrocenyl-4-(2-hydroxyphenyl)-1-methylthio-4-aza-
methylthio-4-aza-1,3-butadiene (9e)
1,3-butadiene (9a)
Orange powder, yield 0.460 g (30%), m.p. 171–173 °C. IR (KBr): m
Orange powder, yield 0.290 g (21%), m.p. 147–148 °C. IR (KBr):
m
483, 594, 693, 735, 814, 899, 934, 1000, 1023, 1039, 1107, 1116,
814, 827, 886, 924, 1001, 1105, 1156, 1230, 1266, 1254, 1284,
1145, 1178, 1258, 1276, 1317, 1385, 1412, 1434, 1448, 1499,
1325, 1374, 1388, 1408, 1420, 1447, 1532, 1621, 2928, 3081,
1651, 2918, 3091, 3395 cmÀ1 1H NMR (400 MHz, CDCl3): d 1.28
.
3099, 3120, 3366 cmÀ1
.
1H NMR (400 MHz, CDCl3): d 2.50 (3H, s,
(9H, s, 3CH3), 2.31 (3H, s, CH3), 4.08 (5H, s, C5H5), 4.28 (5H, s,
C5H5), 3.82, 4.01, 4.13, 4.18, 4.17, 4.22, 4.45, 5.19 (2C5H4), 6.52
(1H, s, HC@), 7.53 (2H, m, C6H3), 7.70 (1H, bs, C6H3), 8.52 (1H, s,
OH). 13C NMR (100 MHz, CDCl3): d 14.11 (CH3), 30.38 (3CH3),
31.47 (C), 68.18, 70.22 (2C5H5), 64.79, 67.58, 68.02, 69.39, 70.45,
70.63, 70.95, 71.97 (2C5H4), 79.95, 83.01 (2CipsoFc), 128.83,
130.93 (C6H3), 132.45 (HC@), 121.17, 124.01, 129.55, 130.72,
CH3), 4.18 (5H, s, C5H5), 4.19 (5H, s, C5H5), 4.27, 4.47, 4.68, 4.73
(2C5H4), 7.05 (1H, s, CH), 7.53 (2H, bs, C6H4), 7.70 (2H, bs, C6H4),
8.10 (1H, s, OH). 13C NMR (100 MHz, CDCl3): d 14.04 (CH3),
69.38, 70.12 (2C5H5), 68.33, 68.80, 71.36, 71.86 (2C5H4), 79.22,
80.06 (2CipsoFc), 128.77, 130.87 (C6H4), 135.22, (HC@), 129.45,
132.38, 135.56, 167.76 (4C). Anal. Calc. for
C30H27Fe2NOS

356
J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
167.81 (5C). Anal. Calc. for C34H35Fe2NOS (617.32): C, 66.15; H,
5.72; N, 2.27; S, 5.18. Found: C, 61.99; H, 4.50; N, 11.46%. MS (El,
70 eV): m/z 617 [M]+.
1447, 1532, 1621, 1738, 2883, 2970, 2981, 3080, 3099, 3120,
3363 cmÀ1 1H NMR (400 MHz, CDCl3): d 1.75 (1H. bs, OH), 2.26
.
(3H, s, CH3), 2.93 (1H, dd, J = 6.0, 9.9 Hz, CH2), 3.02 (1H, dd,
J = 4.2, 9.9 Hz, CH2), 3.61 (2H, m, CH2), 3.81 (1H, m, CH), 4.03
(5H, s, C5H5), 4.21 (5H, s, C5H5), 4.16 (1H, m, C5H4), 4.27 (1H, m,
C5H4), 4.32 (3H, m, C5H4), 4.55 (2H, m, C5H4), 4.84 (1H, m, C5H4)
(2C5H4), 5.50 (1H, s, CH), 7.29–7.35 (5H, m, C6H5). 13C NMR
(100 MHz, CDCl3): d 18.51 (CH3), 30.35, 39.77 (2CH2), 64.70,
70.88 (2CH), 69.16, 69.31 (2C5H5), 65.93, 67.16, 67.20, 68.06,
68.39, 69.53, 69.59, 69.81 (2C5H4), 82.56, 84.59 (2CipsoFc), 126.04,
128.38, 129.38 (C6H5), 125.95, 139.65, 170.12 (3C). Anal. Calc. for
2.3.12. trans-2,3-Diferrocenyl-3-methylthioacrylaldehyde (10a)
Orange powder, yield 0.056 g (4.7%), m.p. 153–155 °C. IR (KBr):
m
485, 522, 688, 742, 809, 822, 870, 960, 1003, 1026, 1043, 1101,
1220, 1270, 1355, 1372, 1412, 1443, 1454, 1565, 1637, 1734,
2928, 2920, 2956, 3006, 3028, 3079, 3100 cmÀ1 1H NMR
.
(400 MHz, CDCl3): d 1.97 (3H, s, CH3), 4.19 (5H, s, C5H5), 4.35
(5H, s, C5H5), 4.37, 4.57, 4.68, 4.84 (2C5H4), 9.41 (1H, s, C@O). 13C
NMR (100 MHz, CDCl3): d 19.96 (CH3), 69.83, 70.39 (2C5H5),
69.71, 70.39, 71.64, 72.04 (2C5H4), 82.37, 83.90 (2CipsoFc), 188.06
(C@O), 134.55, 165.10 (2C). Anal. Calc. for C24H22Fe2OS (470.12):
C, 61.31; H, 4.72; S, 6.81. Found: C, 61.01; H, 4.26; S, 6.51%. MS
(El, 70 eV): m/z 470 [M]+.
C
33H33Fe2NO2S (619.36): C, 64.00; H, 5.37; N, 2.26; S, 5.18. Found:
C, 64.10; H, 5.40; N, 2.36, S, 5.40%. MS (El, 70 eV): m/z 620 [M]+.
2.3.17. E,Z-2,3-Diferrocenyl-6-hydroxy-1-methylthio-4-aza-1,3-
hexadiene (14a)
Orange powder, yield 0.38 g (30%), m.p. 145–147 °C. IR (KBr):
m
2.3.13. cis-2,3-Diferrocenyl-3-methylthioacrylaldehyde (10b)
Orange powder, yield 0.028 g (2.7%), m.p. 145–147 °C. 1H NMR
(400 MHz, CDCl3): d 2.55 (3H, s, CH3), 4.06 (5H, s, C5H5), 4.14 (5H, s,
C5H5), 4.11, 4.16, 4.31, 4.38 (2C5H4), 10.15 (1H, s, HC@O). 13C NMR
(100 MHz, CDCl3): d 23.80 (CH3), 68.50, 69.43 (2C5H5), 68.05, 69.38,
69.54, 70.72 (2C5 H4), 82.79, 83.98 (2CipsoFc), 189.13 (HC@O),
132.44, 162.50 (2C).
817, 1001, 1039, 1106, 1117, 1188, 1249, 1266, 1289, 1326, 1353,
1397, 1451, 1488, 1631, 3027, 3086, 3405 cmÀ1 1H NMR
.
(400 MHz, CDCl3): d 1.84 (1H, bs, OH), 2.50 (3H, s, CH3), 3.57 (2H,
m, CH2), 3.84 (2H, m, CH2), 4.10 (5H, s, C5H5), 4.21, 4.23, 4.27,
4.33, 4.35, 4.37, 4.55, 4.80 (2C5H4), 6.14 (1H, s, HC@). 13C NMR
(100 MHz, CDCl3): d 18.78 (CH3), 55.15, 62.81 (2CH2), 69.38,
69.60 (2C5H5), 68.28, 68.41, 68.61, 69.70, 69.85, 69.94, 70.14,
71.10 (2C5H4), 81.85, 84.08 (2CipsoFc), 126.55, (HC@), 131.05,
171.53 (2C). Anal. Calc. for C26H27Fe2NOS (513.18): C, 60.85; H,
5.30; N, 2.73; S, 6.23. Found: C, 61.12; H, 5.42; N, 3.05; S, 6.41%.
MS (EI, 70 eV): m/z 514 [M]+.
2.3.14. S,R-5,6-Diferrocenyl-7-methylthio-2-phenyl-2,3,6,7-
tetrahydro-1,4-oxazepin-6-ol (13b)
Orange powder, yield 0.42 g (28%), m.p. 182–183 °C. IR (KBr):
m
470, 632, 731, 764, 812, 871, 923, 1000, 1028, 1103, 1119, 1138,
1164, 1205, 1239, 1276, 1304, 1353, 1387, 1420, 1443, 1634,
2.3.18. E,Z-2,3-Diferrocenyl-6-hydroxy-1-methylthio-5-phenyl-4-aza-
1,3-hexadiene (14b)
1711, 2819, 2867, 2939, 2961, 3092, 3357, 3411 cmÀ1
.
1H NMR
(400 MHz, CDCl3): d 1.75 (1H, bs, OH), 2.05 (3H, s, CH3), 3.76 (2H,
m, CH2), 4.03 (5H, s, C5H5), 4.29 (5H, s, C5H5), 4.12, 4.19, 4.21,
4.26, 4.32, 4.68, 4.80, 5.03 (2C5H4), 4.91 (1H, m, CH), 5.44 (1H, s,
CH), 7.28 (1H, m, C6H5), 7.36 (2H, t, J = 7.2 Hz, C6H5), 7.42 (2H, d,
J = 7.2 Hz, C6H5). 13C NMR (100 MHz, CDCl3): d 18.31 (CH3), 67.04
(CH2), 69.08, 69.27 (2C5H5), 67.38, 68.61, 68.74 69.03 (2C5H4),
69.48, 71.00 (2CH), 82.10, 83.60 (2CipsoFc), 126.97, 127.32, 128.46
(C6H5), 81.70, 130.84, 167.73 (3C). Anal. Calc. for C32H31Fe2NO2S
(605.33): C, 63.49; H, 5.16; N, 2.31; S, 5.30. Found: C, 63.90; H,
4.80; N, 2.46, S, 5.50%. MS (El, 70 eV): m/z 605 [M]+.
Orange powder, yield 0.43 g (29%), m.p. 173–174 °C. IR (KBr): m
817, 898, 912, 1000, 1106, 1177, 1210, 1275, 1343, 1377, 1435,
1451, 1485, 1599, 2867, 2919, 2951, 3026, 3086, 3418,
3565 cmÀ1 1H NMR (400 MHz, CDCl3): d 1.70 (1H, bs, OH), 2.41
.
(3H, s, CH3), 3.73 (2H, m, CH2), 4.04 (5H, s, C5H5), 4.17 (5H, s,
C5H5), 4.20, 4.27, 4.55, 4.94 (2C5H4), 4.35 (1H, m, CH), 5.87 (1H, s,
HC@), 7.36 (3H, m, C6H5), 7.43 (2H, m, C6H5). 13C NMR (100 MHz,
CDCl3): d 18.57 (CH3), 38.71 (CH2), 69.20, 69.40 (2C5H5), 60.45
(CH), 67.44, 68.11, 68.15, 68.47, 69.82, 70.07, 70.63, 72.94
(2C5H4), 81.52, 81.79 (2CipsoFc), 125.93, 126.52, 128.26 (C6H5),
130.85, (HC@), 130.94, 143.06, 167.73 (3C). Anal. Calc. for C32H31
-
2.3.15. S,R-5,6-Diferrocenyl-7-methylthio-3-phenyl-2,3,6,7-
tetrahydro-1,4-oxazepin-6-ol (13d)
Fe2NOS (589.27): C, 65.22; H, 5.30; N, 2.38; S, 5.43. Found: C,
65.35; H, 5.48; N, 2.30; S, 5.57%. MS (El, 70 eV): m/z 590 [M]+.
Orange powder, yield 0.48 g (32%), m.p. 181–183 °C. IR (KBr):
m
475, 645, 727, 764, 815, 868, 912, 1001, 1026, 1105, 1116, 1144,
2.3.19. E,Z-2,3-Diferrocenyl-6-hydroxy-5-isopropyl-1-methylthio-4-
1160, 1208, 1253, 1272, 1296, 1357, 1377, 1421, 1456, 1627,
aza-1,3-hexadiene (14c)
1709, 2808, 2852, 2893, 2933, 2958, 3092, 3374, 3401 cmÀ1
.
1H
Orange powder, yield 0.44 g (32%), m.p. 159–160 °C. IR (KBr):
803, 814, 1000, 1025, 1036, 1106, 1161, 1249, 1292, 1313, 1322,
1407, 1499, 1572, 1595, 1622, 2875, 2936, 3091, 3415 cmÀ1 1H
m
NMR (400 MHz, CDCl3): d 2.05 (3H, s, CH3), 2.65 (1H, bs, OH),
3.89 (2H, m, CH2), 4.04 (5H, s, C5H5), 4.30 (5H, s, C5H5), 4.18 (4H,
m, C5H4) 4.26 (1H, m, C5H4) , 4.34 (1H, m, C5H4), 4.68 (1H, m, C5
H4), 5.02 (1H, m, C5H4), 4.92 (1H, dd, J = 4.2, 7,2 Hz , CH), 5.45
(1H, s, CH), 7.28 (1H, m, C6H5), 7.37 (2H, t, J = 7.2 Hz, C6 H5), 7.45
(2H, d, J = 7.2 Hz, C6H5). 13C NMR (100 MHz, CDCl3): d 18.38
(CH3), 67.45 (CH2), 69.24, 69.34 (2C5H5), 67.09, 68.12, 68.61,
68.68, 68.81, 69.10, 69.52, 69.90 (2C5H4), 70.02, 71.06 (2CH),
81.76, 83.70 (2CipsoFc), 127.02, 127.38, 128.53 (C6H5), 130.28,
143.66, 172.02 (3C). Anal. Calc. for C32H31Fe2NO2S (605.27): C,
63.49; H, 5.16; N, 2.48; S, 5.29. Found: C, 63.38; H, 5.22, N, 2.28,
S, 5.50%. MS (El, 70 eV): m/z 605 [M]+.
.
NMR (400 MHz, CDCl3): d 0.98 (3H, d, J = 5.1 Hz, CH3), 1.02 (3H,
d, J = 5.1 Hz, CH3), 1.64 (1H, bs, OH), 2.49 (3H, s, CH3), 3.43 (1H,
m, J = 2.7, 5.4, Hz, CH), 3.54 (1H, dd, J = 3.0, 8.1 Hz, CH2), 3.72
(1H, dd, J = 3.0, 8.1 Hz, CH2), 3.81 (1H, m, CH), 4.14 (5H, s, C5H5),
4.23 (5H, s, C5H5), 4.28, 4.34, 4.38, 4.40, 4.44, 4.45, 4.47, 4.87
(2C5 H4), 6.17 (1H, s, HC@). 13C NMR (100 MHz, CDCl3): d 18.68
(CH3), 19.26, 20.14 (2CH3), 29.67 (CH), 30.65 (CH2), 67.55 (CH),
69.20, 69.25 (2C5H5), 67.87, 68.29, 68.46, 69.91 (2C5H4), 82.62,
82.74 (2CipsoFc), 126.78 (HC@), 131.04, 169.18 (2C). Anal. Calc. for
C29H33Fe2NOS (555.25): C, 62.73; H, 6.00; N, 2.52; S, 5.76. Found:
C, 62.47; H, 5.50; N, 2.47, S, 5.43%. MS (El, 70 eV): m/z 555 [M]+.
2.3.16. S,R-3-Benzyl-5,6-diferrocenyl-7-methylthio-2,3,6,7-
tetrahydro-1,4-oxazepin-6-ol (13e)
2.3.20. E,Z-2,3-Diferrocenyl-6-hydroxy-1-methylthio-6-phenyl-4-aza-
Orange powder, yield 0.52 g (33%), m.p. 178–180 °C. IR (KBr):
m
1,3-hexadiene (14d)
475, 519, 761, 815, 827, 886, 924, 966, 1001, 1028, 1045, 1061,
Orange powder, yield 0.49 g (34%), m.p. 167–168 °C. IR (KBr):
m
1105, 1155, 1230, 1254, 1283, 1326, 1374, 1387, 1408, 1420,
488, 522, 759, 791, 816, 889, 947, 1000, 1022, 1046, 1087, 1106,

J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
357
1174, 1207, 1248, 1296, 1307, 1339, 1374, 1388, 1409, 1451, 1492,
1589, 1607, 2809, 2886, 2923, 3022, 3057, 3088, 3202 cmÀ1 1H
2.3.25. Z,E-2,3-Diferrocenyl-6-hydroxy-1-methylthio-6-phenyl-4-aza-
1,3-hexadiene (15d)
.
NMR (400 MHz, CDCl3): d 1.65 (1H, bs, OH), 2.36 (3H, s, CH3),
3.68 (1H, dd, J = 6.9, 10.5 Hz, CH2), 3.86 (1H, dd, J = 2.7, 10.5 Hz,
CH2), 3.96 (5H, s, C5H5), 3.99 (5H, s, C5H5), 3.94, 4.26, 4.30, 4.47
(2C5 H4), 5.01 (1H, dd, J = 2.4, 6.9 Hz, CH), 6.48 (1H, s, HC@), 7.27
(1H, t, J = 3.0 Hz, C6H5), 7.37 (2H, td, J = 3.0, 5.4 Hz, C6H5), 7.50
(2H, d, J = 3.0 Hz, C6H5). 13C NMR (100 MHz, CDCl3): d 17.70,
(CH3), 61.90 (CH2), 69.52, 69.55 (2C5H5), 66.95, 66.98, 68.10,
68.17 (2C5 H4), 73.59 (CH), 82.81, 84.50 (2CipsoFc), 124.56, 126.13,
128.30 (C6H5), 127.43, (HC@), 128.76, 142.51 167.73 (3C). Anal.
Calc. for C32H31Fe2NOS (589.27): C, 65.22; H, 5.30; N, 2.38; S,
5.43. Found: C, 65.41; H, 5.20; N, 2.10, S, 5.60%. MS (El, 70 eV):
m/z 590 [M]+.
Orange powder, yield 0.19 g (13%), m.p. 180–181 °C. 1H NMR
(400 MHz, CDCl3): d 1.65 (1H, bs, OH), 2.39 (3H, s, CH3), 3.56 (1H,
dd, J = 6.6, 10.5 Hz, CH2), 3.78 (1H, dd, J = 2.4, 10.5 Hz, CH2), 4.10
(10H, s, 2C5H5), 3.94, 4.04, 4.20, 4.32 (2C5 H4), 6.31 (1H, bs, OH),
5.09 (1H, dd, J = 2.4, 6.9 Hz, CH), 6.47 (1H, s, HC@), 7.27 (1H, t,
J = 6.0 Hz, C6H5), 7.36 (2H, td, J = 3.0, 6.0 Hz, C6H5), 7.49 (2H, d,
J = 6.0 Hz, C6H5). 13C NMR (100 MHz, CDCl3): d 17.65 (CH3), 61.44
(CH2), 69.71 (2C5 H5), 66.81, 66.92, 67.88, 68.01, 68.52 (2C5 H4),
73.59 (CH), 84.49, 82.81 (2CipsoFc), 124.81, 125.99, 128.30 (C6H5),
127.35 (HC@), 130.84, 142.66, 167.73 (3C).
2.3.26. Z,E-2,3-Diferrocenyl-6-hydroxy-1-methylthio-7-phenyl-4-aza-
1,3-heptadiene (15e)
2.3.21. E,Z-2,3-Diferrocenyl-6-hydroxy-1-methylthio-7-phenyl-4-aza-
Orange powder, yield 0.15 g (10%), m.p. 183–185 °C. 1H NMR
(400 MHz, CDCl3): d 1.75 (1H, s, OH), 2.41 (3H, s, CH3), 3.49 (1H,
m, CH2), 3.76 (2H, m, CH2), 3.81 (1H, m, CH2), 4.04 (5H, s, C5H5),
4.17 (5H, s, C5H5), 4.20, 4.27, 4.35, 4.54 (2C5 H4), 4.94 (1H, m,
CH), 5.88 (1H, s, HC@), 7.34–7.50 (5H, m, C6H5). 13C NMR
(100 MHz, CDCl3): d 18.58 (CH3), 60.43, 67.38 (2CH2), 69.31,
69.41 (2C5H5), 68.15, 68.33, 68.44, 69.84, 69.89, 70.03, 70.09,
70.65 (2C5H4), 73.82 (CH), 81.52, 81.79 (2CipsoFc), 125.94, 128.26
(C6H5), 128.30, (HC@), 126.65, 130.43, 143.06 (3C).
1,3-heptadiene (14e)
Orange powder, yield 0.47 g (31%), m.p. 175–176 °C. IR (KBr):
816, 868, 979, 1001, 1034, 1079, 1106, 1276, 1343, 1379, 1432,
m
1452, 1490, 1582, 1600, 2861, 2918, 3081, 3094, 3345,
3552 cmÀ1 1H NMR (400 MHz, CDCl3): d 1.75 (1H, s, OH), 2.46
.
(3H, s, CH3), 3.52 (1H, m, CH2), 3.74 (2H, m, CH2), 3.83 (1H, m,
CH2), 4.07 (5H, s, C5H5), 4.13 (5H, s, C5H5), 4.23, 4.32 , 4.36, 4.44,
4.56, 4.65, 4.80, 4.85 (2C5H4), 4.95 (1H, m, CH), 6.01 (1H, s, HC@),
7.34–7.50 (5H, m, C6H5). 13C NMR (100 MHz, CDCl3): d 18.64
(CH3), 61.07, 67.75 (2CH2), 69.23, 69.41 (2C5H5), 67.45, 68.33,
70.24, 72.93 (2C5H4), 73.82 (CH), 83.77, 83.87 (2CipsoFc), 126.14,
127.20 (C6H5), 127.46, (HC@), 126.34, 130.93, 142.64 (3C). Anal.
Calc. for C33H33Fe2NOS (603.29): C, 65.69; H, 5.51; N, 2.32; S,
5.31. Found: C, 61.99; H, 4.50; N, 11.46%. MS (El, 70 eV): m/z 603
[M]+.
2.4. Single-crystal X-ray diffraction data
Suitable single crystals of the compounds 7b, 14a, 14c and 14d
were studied by single-crystal X-ray diffraction. Each crystal was
mounted on a glass fiber and crystallographic data were collected
with an Oxford Diffraction Gemini ‘‘A” diffractometer with a CCD
2.3.22. Z,E-2,3-Diferrocenyl-6-hydroxy-1-methylthio-4-aza-1,3-
hexadiene (15a)
area detector (k Mo K
were determined with a set of three runs of 15 frames (1° in
a
= 0.71073 Å) at 130 K. Unit cell parameters
).
Orange powder, yield 0.13 g (10%), m.p. 145–147 °C. 1H NMR
(400 MHz, CDCl3): d 1.84 (1H, bs, OH), 2.41 (3H, s, CH3), 3.54 (2H,
m, CH2), 3.82 (2H, m, CH2), 4.07 (5H, s, C5H5), 4.24 (5H, s, C5H5),
4.15, 4.18, 4.22, 4.25, 4.38, 4.40, 4.55, 4.70 (2C5H4), 6.48 (1H, s,
HC@). 13C NMR (100 MHz, CDCl3): d 18.23 (CH3), 55.17, 62.81
(2CH2), 69.38, 69.60 (2C5H5), 68.28, 68.41, 68.61, 69.70, 69.85,
69.94, 70.14, 71.10 (2C5 H4), 81.85, 84.08 (2CipsoFc), 124.48,
(HC@), 131.05, 171.53 (2C).
x
The double pass method of scanning was used to exclude any
noise. The collected frames were integrated by using an orientation
matrix determined from the narrow frame scans. CRYSALISPRO and
CRYSALIS RED software packages [30] were used for data collection
and integration. Analysis of the integrated data did not reveal
any decay. Final cell parameters were determined by a global
refinement of 3995, 5415, 4481 and 3897 reflections for 7b, 14a,
14c and 14d respectively. Collected data were corrected for
absorption effects by analytical numeric absorption correction
[31] using a multifaceted crystal model based on expressions upon
the Laue symmetry using equivalent reflections. Structure solution
and refinement were carried with the programs SHELXS-2014 [32] and
2.3.23. Z,E-2,3-Diferrocenyl-6-hydroxy-1-methylthio-5-phenyl-4-aza-
1,3-hexadiene (15b)
Orange powder, yield 0.16 g (11%), m.p. 162–163 °C. 1H NMR
(400 MHz, CDCl3): d 1.70 (1H, bs, OH), 2.47 (3H, s, CH3), 3.52 (1H,
m, CH2), 3.80 (1H, m, CH2), 4.07 (5H, s, C5H5), 4.13 (5H, s, C5H5),
4.35 (1H, m, CH), 4.22, 4.32, 4.38, 4.80 (2C5H4), 6.02 (1H, s, HC@),
7.30–7.46 (5H, m, C6H5). 13C NMR (100 MHz, CDCl3): d 18.64
(CH3), 30.35 (CH2), 61.08 (CH), 69.23, 69.45 (2C5H5), 67.38, 67.88,
68.33, 68.43, 69.87, 70.01, 70.23, 73.83 (2C5H4), 83.80, 83.89
(2CipsoFc), 126.13, 127.46, 128.30 (C6H5), 130.45 (HC@), 132.42,
142.64, 171.29 (3C).
SHELXL-2014 respectively [33], WINGX V2018.3 [34], and MERCURY CSD 4.1.0
[35] were used to prepare the material for publication. Full-matrix
least-squares refinement was carried out by minimizing (Fo2 -
À Fc2)2. All nonhydrogen atoms were refined anisotropically. For
H atoms of the hydroxy groups were located in a difference map
and refined isotropically with Uiso(H) = À1.5 for HAO. Hydrogen
atoms attached to carbon atoms were placed in geometrically ide-
alized positions and refined as riding on their parent atoms, with
CAH = 0.95–1.00 Å with Uiso(H) = 1.2 Ueq(C) for aromatic, methy-
lene and methyne groups, and Uiso(H) = 1.5 Ueq(C) for methyl
group. Crystal data and experimental details of the structure deter-
mination are listed in Table 1. Select bond lengths and angles are
presented in Table 2. Crystallographic data have been deposited
with the Cambridge Crystallographic Data Center as Supplemen-
tary Materials CCDC 1909613 (7b), CCDC 1909614 (14d), CCDC
1909615 (14a) and CCDC 1909616 (14c). Copies of the data can
be obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK. E-mail: deposit@ccdc.cam.ac.uk.
2.3.24. Z,E-2,3-Diferrocenyl-6-hydroxy-5-isopropyl-1-methylthio-4-
aza-1,3-hexadiene (15c)
Orange oil, yield 0.14 g (10%). 1H NMR (400 MHz, CDCl3): d 0.75
(3H, d, J = 5.1 Hz, CH3), 0.89 (3H, d, J = 5.1 Hz, CH3), 1.64 (1H, bs,
OH), 2.50 (3H, s, CH3), 3.57 (2H, m, CH2), 3.84 (2H, m, CH2), 4.13
(5H, s, C5H5), 4.24 (5H, s, C5H5), 4.12, 4.20, 4.28, 4.37, 4.40, 4.47,
4.37, 4.94 (2C5 H4), 6.28 (1H, s, HC@). 13C NMR (100 MHz, CDCl3):
d 18.78 (CH3), 55.15, 62.81 (2CH2), 69.38, 69.60 (2C5H5), 67.64,
67.78, 68.15, 68.28, 68.77, 69.94, 70.17, 70.63 (2C5H4), 81.85,
84.08 (2CipsoFc), 126.55 (HC@), 131.48, 171.53 (2C).

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J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
Table 1
Crystal data and structure refinement parameters for compounds 7b and 14a,c,d.
Identification code
7b
14a
14c
14d
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
C
31H29Fe2NO2S
C26H27Fe2NOS
513.24
130(2)
0.71073
monoclinic
P 21/n
C29H33Fe2NOS
555.32
130(2)
C32H31Fe2NOS
589.34
130(2)
0.71073
orthorhombic
P 21 21 21
591.31
130(2)
0.71073
trÀiclinic
0.71073
trÀiclinic
P 1
P 1
Unit cell dimensions
a (Å)
b (Å)
c (Å)
10.6889(8)
11.1538(10)
11.4826(9)
85.299(7)
78.789(7)
70.111(8).
10.1262(9)
10.1375(9)
22.1983(18)
90
102.186(8)
90
9.8440(8)
11.0566(5)
13.5327(5)
17.7647(7)
90
90
90
11.3703(8)
12.0747(7)
112.950(6)
98.569(6)
91.359(6)
1225.66(16)
2
a
(°)
b (°)
c
(°)
V (Å3)
1262.57(19)
2
2227.4(3)
4
2658.05(19)
4
Z
DCalc. mg m3)
Absorption coefficient
F(0 0 0)
1.555
1.531
1.505
1.473
1.263 mmÀ1
612
1.415 mmÀ1
1064
1.292 mmÀ1
580
1.197 mmÀ1
1224
Crystal size (mm)
h range for data collection
Index ranges
0.570 Â 0.440 Â 0.150
3.569–30.088°
À14 ꢁ h ꢁ 14,
À14 ꢁ k ꢁ 15,
À16 ꢁ l ꢁ 15
13 404
0.250 Â 0.190 Â 0.130
3.460–29.474°
À13 ꢁ h ꢁ 12,
À13 ꢁ k ꢁ 12,
À30 ꢁ l ꢁ 29
19 029
0.510 Â 0.360 Â 0.150
3.445–29.504°
À12 ꢁ h ꢁ 11,
À14 ꢁ k ꢁ 14,
À16 ꢁ l ꢁ 16
11 540
0.250 Â 0.200 Â 0.060
3.530–29.511°
À8 ꢁ h ꢁ 14,
À12 ꢁ k ꢁ 18,
À22 ꢁ l ꢁ 24
9309
Reflections collected
Independent reflections
Maximum and minimum
transmission
6317 [Rint = 0.0326]
0.838 and 0.641
5474 [Rint = 0.0362]
0.847 and 0.767
5758 [Rint = 0.0339]
0.420 and 0.149
5839 [Rint = 0.0275]
0.930 and 0.773
Refinement method
full-matrix least-squares on F2
full-matrix least-squares on
F2
full-matrix least-squares on
F2
full-matrix least-squares on
F2
Data/restraints/parameters
6317/685/344
1.058
5474/4/298
1.056
5758/1/313
1.077
5839/1/338
1.036
Goodness-of-fit on F2
Final R indices [I > 2
R indices (all data)
r
(I)]
R1 = 0.0424, wR2 = 0.0810
R1 = 0.0645, wR2 = 0.0941
0.496 and À0.503
R1 = 0.0391, wR2 = 0.0800
R1 = 0.0588, wR2 = 0.0900
0.679 and À0.685
R1 = 0.0458, wR2 = 0.1150
R1 = 0.0573, wR2 = 0.1271
1.516 and À0.835
R1 = 0.0300, wR2 = 0.0594
R1 = 0.0362, wR2 = 0.0627
0.277 and À0.330
Largest diff. peak and hole (e ÅÀ3
)
C@N, OH, and other fragments. The 1H NMR spectra of compounds
7a–e contain the signals for two ferrocenyl substituents, a signal
for the methylsulfanyl groups, multiplet protons of the CH2, CH,
Ar fragments, as well as the signals from the hydrogen atoms of
the hydroxyl groups. An important feature of the 1H NMR spectra
of compounds 7a–e is the presence of the signals from the hydro-
gen atoms of the methine groups (CHASMe) shifted upfield
(d = 5.44–5.50 ppm).
The spatial structure of oxazepine 7b was also determined by X-
ray diffraction analysis of single crystals obtained using crystalliza-
tion from CH2Cl2. The perspective view of molecule 7b is shown in
Fig. 1a; the crystal packing shows in Fig. 1b; and the main geomet-
rical parameters of the compound are listed in Table 1. The seven-
membered ring in molecule 7b is stabilized in a boat conformation,
with two heteroatoms N and O occupying positions 1 and 4 in the
heterocycle. X-ray analysis showed that compound 7b has the
structure of S,R/R,S-5,6-diferrocenyl-6-hydroxy-7-methylthio-3-
phenyl-6,7-dihydro-1,4-oxazepine, where the ferrocene and
methylthio substituents occupy the axial–equatorial positions.
Data from the X-ray analysis show that the C@N bond in the
oxazepine ring is somewhat longer (1.279(3) Å) than the standard
value of 1.23 Å [38]. The lengths of the CAFe and CAC bonds in the
ferrocenyl substituents as well as the geometric parameters of the
ferrocene sandwiches are close to standard values [39].
3. Results and discussion
The initial 2,3-diferrocenyl-1-methylthiocyclopropenylium
iodide 2 was synthesized via the methylation of 2,3-diferrocenyl-
cyclopropenethione 1 using methyl iodide (Scheme 1):
Cyclopropenethione 1 was obtained in this study using direct
sulfonation of 2,3-diferrocenylcyclopropenone by Lawesson’s
reagent [36,37] with a yield of ꢀ90–95%. In earlier work we pub-
lished a method for synthesizing diferrocenylcyclopropenethione
1 using a three-stage synthesis according to Scheme 2 [25]:
We found that cyclopropropenylium iodide 2 interacts with 1,2-
aminophenols 3a–e in dry benzene upon boiling (about 6–8 h) in
the presence of Et3N, forming the following products: 1,1-
dimethylthio-2,3-diferrocenylcyclopropene 4, 2-ferrocenylbenzox-
azoles 5a–e, 2-(cis/trans-1,2-diferrocenylvinyl)oxazoles 6a–e, 3,
4-diferrocenyl-2-methylthio-2,3-dihydro-benzo[b]-1,4-oxazepin-3-
oles 7a–e, 3,4-diferrocenylquinolin-8-ols 8b–c, E-/Z-2,3-diferro-
cenyl-4-(2-hydroxy-phenyl)-1-methylthio-4-aza-1,3-dienes 9a–e
and
cis-/trans-2,3-diferrocenyl-3-methylthiopropanal
10a,b
(Scheme 3).
All the compounds were separated using column and thin-layer
chromatography (Al2O3, Brockmann activity III), and their struc-
tures were established using IR, 1H and 13C NMR spectroscopy, as
well as elemental analysis. The physicochemical characteristics of
compounds 4, 5a–e, 6a–e and 8c,d, which have been described ear-
lier[28], fully match the literature data. According to the 1H NMR
spectra of novel compounds 7a–e, despite the presence of two chi-
ral centers in the molecules, they were formed as a single diastere-
omers, which suggests the stereospecificity of the process.
2,3-Diferrocenyl-4-(2-hydroxyphenyl)-1-methylthio-4-aza-1,3-
dienes 9a–e was also isolated using column chromatography and
thin-layer chromatography (Al2O3, Brockmann activity III). 4-Aza-
1,3-dienes 9a–e are orange crystalline compounds, which during
storage decompose fairly quickly. The structures of compounds
9a–e were established based on the data obtained from IR, 1H
and 13C NMR spectroscopy, elemental analysis, and mass spec-
The IR spectra of compounds 7a–e contain the corresponding
numbers of characteristic absorption bands of the Ferrocenyl, Ar,

J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
359
The 1H NMR spectra of compounds 9a–e contain one singlet for
the methylthio fragments, characteristic signals for two ferrocenyl
substituents, one singlet for the olefinic proton and signals from
the protons of the aryl groups. The characteristic singlets of the
olefinic protons and protons of the hydroxyl groups of compounds
9a–e are located downfield (d = 7.05–7.47 and 7.71–8.10 ppm,
respectively). The 13C NMR spectra of compounds 9a–e contain
the necessary numbers of signals from the carbon atoms of the fer-
rocenylic, arylic, olefinic fragments of the molecules 9a–e, as well
Table 2
Selected bond lengths and bond angles for compounds 7b and 14a,c,d.
Selected bond lengths (Å)
Selected bond angles (°)
7b
C(6)AO(1)
C(6)AC(11)
C(6)AC(7)
C(7)AO(2)
C(7)AS(1)
C(9)AO(2)
C(9)AC(10)
C(10)AN(1)
C(11)AN(1)
1.428(3)
C(11)AC(6)AC(7)
O(2)AC(7)AS(1)
O(2)AC(9)AC(10)
C(22)AC(10)AN(1)
C(9)AC(10)AN(1)
N(1)AC(11)AC(12)
N(1)AC(11)AC(6)
C(11)AN(1)AC(10)
C(9)AO(2)AC(7)
C(8)AS(1)AC(7)
110.8(2)
113.67(17)
127.2(2)
112.5(2)
130.6(2)
115.3(2)
124.8(2)
128.4(2)
121.90(19)
101.6(7)
1.535(3)
1.547(3)
1.409(3)
1.813(3)
1.382(3)
1.407(3)
1.409(3)
1.279(3)
as from the quaternary carbons, and the signals from the two Cipso
-
Fc atoms, confirming their diene structure. In addition, the IR spec-
tra of compounds 9a–e contain bands at ꢀ3400 cmÀ1, which are
characteristic of OH groups. Presumably, 4-(2-hydroxyphenyl)-4-
aza-1,3-dienes 9a–e have an 1-E-configuration analogous to those
of E-2,3-diferrocenyl-1-methylthio-1,3-diene [21].
Optimal results in the synthesis of compounds 7a–e (23–30%)
and 9a–e (24–30%) were obtained when the reaction mixtures (2
+ 3a–e = 1:1.3) were heated to ꢀ80–82 °C for 8 h in benzene
(Table 3). The highest results of the benzoxazoles 6a–e (32–38%)
[28] and 2,3-diferrocenylacroleins 10a + 10b (16–19%) were
obtained when the reaction mixtures were boiled (6–8 h) in
acetonitrile.
14a
C(11)AC(21)
C(21)AC(25)
C(21)AC(22)
C(22)AN(1)
C(23)AN(1)
C(23)AC(24)
C(24)AO(1)
C(25)AS(1)
C(26)AS(1)
1.473(3)
1.337(3)
1.506(3)
1.281(3)
1.467(3)
1.509(3)
1.414(3)
1.735(3)
1.790(11)
C(25)AC(21)AC(11)
C(25)AC(21)AC(22)
C(11)AC(21)AC(22)
N(1)AC(22)AC(21)
C(1)AC(22)AC(21)
N(1)AC(23)AC(24)
O(1)AC(24)AC(23)
C(22)AN(1)AC(23)
C(25)AS(1)AC(26)
126.9(2)
119.5(2)
113.62(19)
124.5(2)
115.21(19)
111.16(19)
110.8(2)
119.1(2)
102.8(2)
14c
The side products 4, 5a–e, and 8b–d have been described ear-
lier. The physical and 1H and 13C NMR spectroscopic characteristics
of compounds 4, 5a–e, and 8b–d were in accordance with the lit-
erature data [28,29,40].
We also found that aliphatic 1,4-N,O-nucleophiles 11a–e inter-
act with 2,3-diferrocenyl-1-methylthio-cyclopropenylium iodide 2
under similar conditions (benzene, 80 °C, Et3N), forming a mixture
of the principal products 13b,d,e, 14a–e, 15a–e. In addition, 1,1-
dimethylthio-2,3-diferrocenylcyclopropene 4, 10a–b and 2-(cis-
1,2-diferrocenylvinyl)-4,5 dihydrooxazoles 12a–e [41] were also
isolated from the reaction mixture (Scheme 4).
All the resultant compounds were separated using chromatog-
raphy on (Al2O3, Brockmann activity III) and dry TLC on silica gel.
Analysis of the 1H and 13C NMR spectra showed that compounds
13b,d,e are individual diastereomers of 5,6-diferrocenyl-tetrahy-
dro-1,4-oxazepines, whereas compounds 14a–e and 15a–e are iso-
lated as a mixture of geometric isomers of the 2,3-diferrocenyl-6-
hydroxy-4-aza-1,3-alkadienes, compounds 10a,b – cis- and trans-
2,3-diferrocenylacroleins. The data obtained from IR, 1H and 13C
NMR analysis, mass spectra analysis, and elemental analysis con-
firm the structures attributed to them.
C(6)AN(1)
C(7)AN(1)
C(7)AC(8)
C(7)AC(9)
C(8)AO(1)
C(9)AC(10)
C(12)AC(23)
C(23)AS(1)
C(24)AS(1)
1.282(3)
1.475(3)
1.527(3)
1.554(4)
1.417(3)
1.522(4)
1.347(4)
1.735(3)
1.798(4)
N(1)AC(6)AC(5)
N(1)AC(6)AC(12)
N(1)AC(7)AC(8)
N(1)AC(7)AC(9)
C(8)AC(7)AC(9)
O(1)AC(8)AC(7)
C(12)AC(23)AS(1)
C(6)AN(1)AC(7)
C(23)AS(1)AC(24)
120.1(2)
123.7(2)
109.72(19)
108.3(2)
112.1(2)
111.0(2)
126.8(2)
117.9(2)
100.92(16)
14d
C(6)AN(1)
C(6)AC(15)
C(7)AN(1)
C(7)AC(9)
C(7)AC(8)
C(8)AO(1)
C(15)AC(26)
C(26)AS(1)
C(27)AS(1)
1.274(4)
1.512(4)
1.475(4)
1.509(4)
1.521(4)
1.424(4)
1.342(4)
1.741(3)
1.807(4)
N(1)AC(6)AC(1)
N(1)AC(6)AC(15)
C(1)AC(6)AC(15)
N(1)AC(7)AC(9)
N(1)AC(7)AC(8)
C(9)AC(7)AC(8)
O(1)AC(8)AC(7)
C(15)AC(26)AS(1)
C(6)AN(1)AC(7)
C(26)AS(1)AC(27)
118.6(2)
125.5(3)
115.9(2)
111.4(2)
106.6(2)
110.8(3)
111.7(3)
127.2(2)
118.8(2)
99.21(16)
trometry, and confirmed that dienes 9a–e were obtained in the
form of single geometric isomers.
Scheme 1. Synthesis of the 2,3-diferrocenylcyclopropenthione 1 and 2,3-diferrocenyl-1-methylsulfonyl-cyclopropenylium iodide 2.
Scheme 2. Synthesis of the 2,3-diferrocenylcyclopropenthione.

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J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
Scheme 3. Reactions of the 2,3-diferrocenyl-1-methylsulfonylcyclopropenylium iodide 2 with 1,2-aminophenols 3a–e.
Fig. 1. (a) Crystal structure of 7b; (b) crystal packing of 7b.
Table 3
Optimal reaction conditions for the synthesis of the representative compounds 6a–e, 7a–e, 8b–d, 9a–e, and 10a + b.
Entry
Solvent
2 + 3a–e
4 (%)
5a–e (%)
6a–e (%)
7a–e (%)
8b-d (%)
9a–e (%)
10a + 10b (%)
(1:1.3)
1
2
3
4
5
6
7
8
9
10
Benzene
Benzene
Benzene
Benzene
Benzene
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
2 + 3a
2 + 3b
2 + 3c
2 + 3d
2 + 3e
2 + 3a
2 + 3b
2 + 3c
2 + 3d
2 + 3e
5.0
3.5
4.0
3.5
4.2
7.0
7.5
6.8
7.2
6.5
8.0
6.0
6.0
7.0
6.5
9.0
11.0
10.0
12.0
11.0
17.0
14.0
16.0
14.0
18.0
35.0
32.0
37.0
38.0
35.0
26.0
30.0
25.0
23.0
25.0
–
–
–
–
–
–
24.0
27.0
24.0
26.0
30.0
–
–
–
–
–
7.0
9.0
7.0
8.0
10.0
11.0
9.0
–
7.0
–
17.0
19.0
16.0
17.0
17.5
11.0
12.0
16.0
–
The 5,6-diferrocenyl-6-hydroxy-7-methylthio-2,3,6,7-tetrahy-
dro-1,4-oxazepines 13b,d,e were characterized by their 1H and
13C NMR spectral data, elemental analysis data and coincidence
of their physicochemical properties with those for compounds
7a–e. The 1H NMR spectra of products 13b,d,e contain the charac-
teristic singlets from CH protons of CHSMe fragments and protons
of OH groups with the chemical shift values d = 5.45–5.50 ppm and
d = 1.65–1.75 ppm, respectively. The presence of the corresponding
numbers of the signals from the quaternary carbon atoms, methyl,
methylene, methine, aryl and ferrocenyl groups in the 13C NMR
spectra confirms the cyclic 1,4-oxazepine structure of each
diastereomer 13b,d,e.
The 1H and 13C NMR spectroscopic data of the aliphatic hydrox-
ydienes suggest that they were formed in mixture of two isomeric

J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
361
forms: 14a–e + 15a–e in a ꢀ2:1 ratio. Our attempts to separate the
isomeric dienes by chromatography were unsuccessful, however
they were easily identified by spectroscopy because the positions
of all the signals in the 1H and 13C NMR spectra, their multiplicities,
and integral intensities are distinctly different. The isomers 14a,c,d
were separated partially by TLC on silica gel. The crystal structures
Scheme 4. Reactions of the 2,3-diferrocenyl-1-methylsulfonylcyclopropenylium iodide 2 with 1,2-aminoalcohols 11a–e.
Fig. 2. (a) Crystal structure of E-14a. (b) Crystal packing of E-14a.
Fig. 3. (a) Crystal structure of E-14c. (b) Crystal packing of E-14c.

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J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
of compounds 14a,c,d were established by X-ray diffraction analy-
sis of a single crystals of these compounds, which were prepared
by crystallization in diethyl ether. The perspective views of mole-
cules 14a,c,d are shown in Figs. 2a, 3a, 4a, crystal packing views
of 14a,c,d are displayed in Figs. 2b, 3b, 4b; selected bond lengths
and angles are given in Table 1.
longer [1.281(3) (14a), 1.282(3) (14c), 1.274(4) Å (14d)] than the
standard value of 1.23 Å. [40] According to the X-ray diffraction
data, the crystal structure of the molecule 14a has a S-trans-config-
uration for the double bonds, whereas the crystal structures of the
molecules 14c and 14d have s-cis-configurations for the double
bonds.
The compounds 14a,c,d have the structures of (1-E)-2,3-diferro-
Compounds 10a and 10b were isolated from the reactions of
aromatic and aliphatic bis-1,4-N,O-nucleophiles 3a–e and 11a–e
with 2.3-diferrocenyl-1-methyltiocyclopropenylium iodide 2 as a
mixture of two geometric isomers in ca. 2:1 ratios (10a and 10b
represent cis- and trans-2,3-diferrocenyl-3-methylthio-acroleins),
the 1H NMR spectroscopic data, shows the signs for ferrocenyl
and methylsulfanyl substituents, two low field singlets [d = 10.15
(10a) and 9.41 (10b) ppm] for the CH protons of the HC@O frag-
ments. The 13C NMR spectra of compounds 10a and 10b contained
signals for the carbon atoms of two ferrocenyl units with two sig-
cenyl-1-methylthio-6-hydroxy-4-aza-1,3-dienes.
Obviously,
hydroxydienes 14b,e have an (1-E) configurations analogous to
those of 14a,c,d; isomeric dienes 15a–e have an (1-Z) configura-
tions with trans-orientation of the MeS and Fc substituents in
the FcC@CSMe fragments of the dienic systems.
Data from the X-ray analysis show that the C@C bonds in the
compounds 14a,c,d are somewhat shorter [1.337(3) (14a), 1.347
(4) (14c), 1.342(4) Å (14d)] than the standard value of 1.38 Å
[40] and the C@N bond in the azadienes 14a,c,d are somewhat
Fig. 4. (a) Crystal structure of E-14d. (b) Crystal packing of E-14d.
Scheme 5. Plausible mechanism of the formation of compounds 4, 10a,b and 12a–e.

J.J. Sánchez García et al. / Polyhedron 171 (2019) 353–364
363
nals for CipsoFc, one signal for MeS substituent, one signal for HC@O
fragment, two signals for the quaternary carbon atoms.
atoms of 2,3-diferrocenyl-1-methylthiocyclopropenylium iodide 2
(Scheme 6) with obtention cyclopropane intermediates 23a–e.
The diferrocenylbenzoxazepines 7a–e and N-aryl-4-aza-1,3-dienes
9a–e are formed via a three-membered ring opening giving rise to
carbenes 24a–e and following pathway A and B, respectively. Evi-
dently, compounds 13b,c,d, 14a–e and 15a–e were obtained by
analogy with Scheme 6.
The presumable mechanism describing the formation of the
derivatives of oxazoles 12a–e, 2,3-diferrocenyl-1-methylth-
ioacroleins 10a,b and 2,3-diferrocenyl-1,1-dimethylthio-cyclo-
propene 4 is shown in Scheme 5. The nitrogen atoms of bis-1,4-
N,O-nucleophiles, for example 11a–e, attacks atom C-1 of 2,3-difer-
rocenyl-1-methylthiocyclopropenylium iodide 2 and substitutes
the MeS group with the formation of 1-aminocyclopropenylium
cations 16a–e and MeSH. The repeated attack of another oxygen
atom on the C-1 carbon atom in cations 16a–e yield the spirane
tetrahydrooxazoles 17a–e. The opening of the small cycle ring in
the cyclopropene fragments of 17a–e with the formation of vinyl-
carbene intermediates 18a–e and subsequent intramolecular cyclic
transformation of the carbenes lead to the formation of oxazoles
12a–e. The sulfur atoms of methanethiol attacks the C-1 carbon
4. Conclusions
The results of the present study support our previous conclu-
sion [24,28,29,42], that depending on whether the nucleophile
attacks of C(1) or C(2) on the cation 2 of the initially formed inter-
mediates 16a–e,17a–e, 19, or 23a–e (see Schemes 5 and 6) usually
form the products that either retain the original three-membered
ring or undergo CAC cleavage to give ring-opened products. The
reactions of 2,3-diferroceny-1-methylthiocyclopropenylium iodide
2 with aromatic and aliphatic bis-1,4-N,O-nucleophiles 3a–e and
11a–e, respectively, in a benzene medium in the presence of
Et3N affords products of the nucleophile attacks C(1) and C(2)
atoms of the three-membered 2 giving non-regioselectivity mix-
tures of the seven (from 3a–e) and five (from 11a–e) compounds.
However, in the main were obtained derivatives of the diferro-
cenyl-1,4-oxazepines and diferrocenyl-hydroxy-4-aza-1,3-dienes
7a–e + 9a–e (ꢀ49–57%), 13b,c,d (ꢀ28–33%), 14a–e + 15a–e (ꢀ40–
47%). These were formed by nucleophilic attacks of the C(2) atoms
of the cyclopropenylium cations with nitrogen atoms of the nucle-
ophiles 3a–e or 11a–e. This novel method of synthesis of 1,4-oxa-
zepines and hydroxy-4-aza-1,3-dienes, obviously, requires more
detailed studies aimed at the extension of its potential for the
application in organic synthesis, further investigations in the fields
of theoretical and synthetic organic chemistry, the search for new
methods for an access to practically valuable materials.
atoms of salt
2 with the obtention of 2,3-diferrocenyl-1-
methylthio-cyclopropene 4; which attacks the C-2 carbon atoms
of compound 2 by sulfur atoms of methanethiol are formed tetra-
substituted cyclopropenes 19. The opening of the small cycle ring
in the cyclopropene 19 into 2,3-diferrocenyl-3-methylthiovinyl-
carbene 20 with subsequent intramolecular transformation of 20
in the presence of the water result to cis- and trans-2,3-diferro-
cenyl-1-methylthioacroleins 10a,b.
The formation of diferrocenylbenz-1,4-oxazepines 7a–e and N-
(2-hydroxyphenyl)-4-aza-1,3-dienes 9a–e may be rationalized as
being due to the nucleophilic contacts of the nitrogen atoms of
the bis-1,4-N,O-nucleophiles, for example 3a–e, with C-2 carbon
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by CONACyT (Mexico, grant 251437)
and DGAPA–UNAM (Mexico, grant IN 217318). We are grateful
for the technical assistance by Rene Sebastian Joo Cisneros, Ana
Gabriela Alpizar Mora, Gustavo Huerta Vargas, and Minerva
Monroy.
Appendix A. Supplementary data
CCDC 1909613, 1909614, 1909615 and 1909616 contains the
supplementary crystallographic data for 7b, 14d, 14a and 14c.
These data can be obtained free of charge via http://www.
ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk. Sup-
plementary data to this article can be found online at https://doi.
org/10.1016/j.poly.2019.07.019.
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