Synthesis of ferrocenyl thioketones and their reactions with diphenyldiazomethane

Article abstract of DOI:10.1080/10426507.2015.1071817

A series of ferrocenyl ketones were obtained via the Friedel-Crafts acylation with mixed anhydrides using ferrocene as a nucleophilic agent or ferrocene carboxylic acid as a precursor of the electrophilic species. The ketones obtained thereby undergo smooth thionation (tetrahydrofuran, 65°C) with Lawesson's reagent. The ferrocenyl thioketones react with diphenyldiazomethane via N2 elimination to afford the hitherto unknown ferrocenyl-substituted thiiranes.

Full text of DOI:10.1080/10426507.2015.1071817

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis of Ferrocenyl Thioketones and their
Reactions with Diphenyldiazomethane
Grzegorz Mlostoń, Róża Hamera & Heinz Heimgartner
To cite this article: Grzegorz Mlostoń, Róża Hamera & Heinz Heimgartner (2015)
Synthesis of Ferrocenyl Thioketones and their Reactions with Diphenyldiazomethane,
Phosphorus, Sulfur, and Silicon and the Related Elements, 190:12, 2125-2133, DOI:
10.1080/10426507.2015.1071817
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Date: 21 March 2016, At: 19:11

Phosphorus, Sulfur, and Silicon, 190:2125–2133, 2015
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2015.1071817
SYNTHESIS OF FERROCENYL THIOKETONES AND THEIR
REACTIONS WITH DIPHENYLDIAZOMETHANE
1
1
2
Grzegorz Mlosto n´ , R o´ z˙ a Hamera, and Heinz Heimgartner
1
Department of Organic and Applied Chemistry, University of Ł o´ d z´ , Tamka 12, PL
9
1-403 Ł o´ d z´ , Poland
2
Department of Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057
Zurich, Switzerland
GRAPHICAL ABSTRACT
Abstract A series of ferrocenyl ketones were obtained via the Friedel–Crafts acylation with
mixed anhydrides using ferrocene as a nucleophilic agent or ferrocene carboxylic acid as a
precursor of the electrophilic species. The ketones obtained thereby undergo smooth thiona-
◦
tion (tetrahydrofuran, 65 C) with Lawesson’s reagent. The ferrocenyl thioketones react with
diphenyldiazomethane via N2 elimination to afford the hitherto unknown ferrocenyl-substituted
thiiranes.
Keywords Ferrocene; thioketones; diazo compounds; thiiranes; thiophene derivatives;
selenophene derivatives
INTRODUCTION
Aromatic thioketones are relatively stable compounds, which can be conveniently
1
prepared from corresponding ketones by O/S exchange using Lawesson’s reagent (LR). In
the last three decades, aromatic thioketones and non-enolizable aliphatic thioketones have
been explored extensively as versatile building blocks for the synthesis of more complex
sulfur-containing compounds. Cycloaddition reactions leading to five- and six-membered
S-heterocycles are of special importance, as thioketones are recognized as superdipo-
2
3
larophilic and superdienophilic agents. Moreover, thioketones are unique substrates for
the preparation of differently substituted alkenes via the so-called “two-fold extrusion
reaction” with diazo compounds.4
Received 28 May 2015; accepted 1 July 2015.
Part of the PhD thesis of R o´ z˙ a Hamera, University of Ł o´ d z´ , Ł o´ d z´ , Poland.
This paper is dedicated to Professor Emeritus Robert R. Holmes.
Address correspondence to Grzegorz Mlosto n´ , Department of Organic and Applied Chemistry, University
of Ł o´ d z´ , Tamka 12, 91-403 Ł o´ d z´ , Poland. E-mail: gmloston@uni.lodz.pl
2
125

´
2
126
G. MLOSTON ET AL.
Ferrocenyl-functionalized compounds are of great importance and found applications
5
in materials chemistry, medicinal chemistry, polymer sciences, etc. In spite of growing
6
interest in ferrocenyl-containing S-heterocycles, very little is known about the ferrocenyl-
substituted thioketones, which are attractive substrates for their synthesis. The synthesis
of three representatives, i.e., ferrocenyl phenyl thioketone, ferrocenyl methyl thioketone,
and tert-butyl ferrocenyl thioketones, was reported in 1978 without complete spectroscopic
7
data. In addition, diferrocenyl thioketone was described as the product of thionation of
diferrocenyl ketone.8
In our ongoing studies on the applications of thiocarbonyl compounds for the syn-
thesis of S-heterocycles and related compounds, we reported the synthesis of diverse aryl
hetaryl and dihetaryl thioketones, which are relatively stable and can be stored without
9
decomposition. These results prompted us to elaborate a similar method for the prepa-
ration of ferrocenyl hetaryl ketones and subsequent thionation to give the corresponding
thioketones.
RESULTS AND DISCUSSION
The best method for the preparation of ferrocenyl ketones 1 comprises the
Friedel–Crafts acylation, and in the case of differocenyl ketone, the reported reaction was
performed starting with ferrocene and ferrocenoyl chloride in the presence of AlCl3 used
8
in excess. However, in our hands, this protocol turned out to be inefficient, and in the best
case the desired ketone 1a was obtained in only 25% yield. Therefore, we elaborated a
10
new method based on acylation via the in situ-generated mixed anhydrides. In the case
of 1a, ferrocenyl carboxylic acid was mixed with an equimolar amount of trifluoroacetic
anhydride (TFAA) in the presence of trifluoroacetic acid (TFA) in CH2Cl2 solution at room
temperature. Under these conditions, the added ferrocene underwent smooth acylation
to give 1a in reproducible and satisfactory yield (52%, Scheme 1). The same procedure
was applied for the acylation of N-methylpyrrole and selenophene, leading to the desired
non-symmetric ketones 1b and 1c (84 and 88% yield, respectively).
Scheme 1
A modified procedure was applied for the preparation of ferrocenyl phenyl ketone
1d, as the method presented above was unsuccessful. For that reason, the alternative mixed
anhydride prepared from benzoic acid and TFAA in the presence of an equimolar amount
of triflic acid (TfOH) in CH2Cl2 was prepared in situ at room temperature. Under these

FERROCENYL THIOKETONES AND THEIR REACTIONS
2127
conditions, the added ferrocene underwent benzoylation to afford ketone 1d as 65% yield
Scheme 2).
(
Scheme 2
The transformation of ketones 1 into the corresponding thioketones 2 was smoothly
◦
achieved by their treatment with LR in tetrahydrofuran (THF) at 65 C. The crude products
were purified by column chromatography and isolated as green solids in 75–85% yield
(Scheme 3).
Scheme 3
Aromatic thioketones are known to react with diazomethane and its derivatives at
low temperature, yielding 2,5-dihydro-1,3,4-thiadiazoles as the products of [3+2] cycload-
11
ditions. Upon heating, these cycloadducts eliminate N2 and generate in situ the reactive
thiocarbonyl ylides, which, depending on the type of substituents and the reaction condi-
tions, are converted into thiiranes, 1,4-dithianes, 1,3-dithiolanes, etc. The latter heterocy-
cles were obtained as the sole products from the reaction of diazomethane with hetaryl
9
thioketones. However, in the series of aryl selenophenyl thioketones, the intermediate
thiocarbonyl ylides unexpectedly dimerize to give 12-membered diselenaheterocycles via
a postulated diradical intermediate.12
The test experiments with diazomethane and thioketone 2a were performed in tetrahy-
◦
drofurane (THF) solution at room temperature as well as at –60 C. In both cases, immediate
disappearance of the typical color of thioketone was observed, but after a few minutes at
room temperature, the solutions turned black and no defined products could be isolated.
Similar courseofreactionwasobservedintheattemptedreactionof 2awith2-diazopropane.
Finally, the reaction of 2a with the less reactive diphenyldiazomethane was performed
in THF at room temperature. In this case, the thin layer chromatography (TLC) analysis
evidenced the formation of a single product, which was identified as the symmetrical
diferrocenyl-substituted thiirane 3a on the basis of spectroscopic data (Scheme 4). Thus,
13
in the C NMR spectrum, the diagnostic C-signals of thiirane were found at 64.8 and
9.6 ppm. Similarly, reactions of diphenyldiazomethane with 2b–d occurred smoothly
under the same conditions leading to non-symmetrical thiiranes 3b–d, respectively.
6

´
2
128
G. MLOSTON ET AL.
Scheme 4
It is worth mentioning that the ferrocenyl-substituted thiiranes 3 are stable under
standard conditions and can be used for further applications aimed at the preparation of
more complex ferrocenyl-containing products.
CONCLUSIONS
The method for the preparation of ferrocenyl ketones via the Friedel–Crafts acylation
with trifluoroacetyl-containing mixed anhydrides opens a straightforward access to this
class of compounds. These ketones can be conveniently transformed into the corresponding
aryl/hetaryl ferrocenyl thioketones. Their reactions with reactive diazo compounds, such as
diazomethane or 2-diazopropane, lead to decomposition. On the other hand, the less reactive
diphenyldiazomethane reacts with ferrocenyl thioketones via spontaneous elimination of
N2 to give ferrocenyl-substituted thiiranes as products of 1,3-dipolar electrocyclization of
the intermediate thiocarbonyl ylide.
EXPERIMENTAL
General Methods
All solvents were dried over appropriate drying agents and distilled before use.
Reactions of the prepared ketones and thioketones were carried out under argon. Melting
points were determined in a capillary using a Stewart R SMP30. The IR spectra (KBr
ꢀ
1
13
pellets) were recorded on a Nexus FT-IR spectrometer. The H- and C NMR spectra
were measured on a Bruker Avance III (600 and 150 MHz, respectively) instrument using
CHCl3/CDCl3 signals as references. Electrospray ionization–mass spectra (ESI-MS) were
recorded on a Varian 500-MS IT mass spectrometer. The elemental analyses were recorded
on a Vario Micro Cube. Flash chromatography was carried out using Silica gel 60 (Sigma-
Aldrich, 230–400 mesh). The notation Fc in this study represents ferrocenyl.
Synthesis of Ketones 1a–c (General Procedure)
To a solution of ferrocenecarboxylic acid (2.17 mmol, 0.5 g) in dry CH2Cl2 (10 mL)
was added TFAA (2.17 mmol, 0.3 mL). After stirring the mixture for ca. 2 min at room
temperature, TFA (2.17 mmol, 0.16 mL) and the corresponding hetarene (2.17 mmol) were
added. The progress of the reaction was monitored by TLC. After the completion of the
reaction, water (15 mL) was added. The organic layer was separated and the aqueous
layer was extracted with CH2Cl2. The combined organic extracts were dried (MgSO4),
and the solvent was evaporated. Crude products were purified by flash chromatography
(CH2Cl2/CH3OH, 99:1).

FERROCENYL THIOKETONES AND THEIR REACTIONS
2129
Diferrocenyl Ketone (1a)
o
13
o
Yield: 449 mg (52%). Orange solid, m.p.: 203.1–204.3 C [lit. , m.p. 204 C (decom-
1
position)]. H NMR: δ 4.21 (s, 10H, CH-Fc), 4.53 (t, JH,H = 1.8 Hz, 4H, CH-Fc), 5.00 (t,
13
JH,H = 1.8 Hz, 4H, CH-Fc) ppm. C NMR: δ 70.0, 70.6, 71.4 (18C, CH-Fc), 80.5 (2C,
C-Fc), 199.2 (1C, C=O) ppm. IR: υ 3123 (m), 3105 (m), 3096 (m), 3089 (m), 1772 (w),
1
1
(
(
608 (vs, C=O), 1541 (m), 1465 (vs), 1413 (m), 1395 (m), 1377 (s), 1355 (m), 1293 (vs),
202 (m), 1106 (s), 1064 (s), 1054 (m), 1027 (m), 1009 (m), 904 (m), 836 (s), 819 (s), 807
−1
+
vs), 771 (m), 580 (m), 510 (m), 493 (vs), 478 (vs) cm . ESI-MS 400 (8 [M+2] ), 421
+
+
100 [M+Na] ), 422 (24 [M+Na+1] ).
Ferrocenyl N-methylpyrrol-2-yl Ketone (1b)
o
1
Yield: 534 mg (84%). Red solid, m.p.: 113.9–115.4 C. H NMR: δ 3.97 (s, 3H, CH3),
.22 (s, 5H, CH-Fc), 4.50 (t, JH,H = 1.8 Hz, 2H, CH-Fc), 4.95 (t, JH,H = 1.8 Hz, 2H,
4
CH-Fc), 6.16 (dd, JH,H = 3.6, 2.4 Hz, 1H, CHarom.), 6.84 (dd, JH,H = 2.4, 1.2 Hz, 1H,
13
CHarom.), 7.14 (dd, JH,H = 3.6, 1.2 Hz, 1H, CHarom.) ppm. C NMR: δ 37.2 (1C, CH3),
70.0, 71.0, 71.3 (9C, CH-Fc), 80.8 (1C, C-Fc), 107.6, 118.8, 129.8 (3C, CHarom.), 131.3
(
1C, Carom.), 187.9 (1C, C=O) ppm. 70.4, 71.0, 72.2 (9 CH-Fc), 78.6 (C-Fc), 130.4, 133.4,
1
2
1
37.8 (3 CHarom.), 151.4 (Carom.), 190.5 (C=O) ppm. IR: υ 3118 (w), 3105 (m), 3082 (w),
927 (w), 1600 (vs, C=O), 1524 (m), 1444 (vs), 1405 (vs), 1379 (s), 1320 (m), 1261 (s),
206 (w), 1174 (w), 1066 (m), 1047 (m), 1021 (m), 940 (w), 844 (m), 836 (m), 823 (s), 745
−1
+
+
(
vs), 609 (m), 565 (m), 503 (s), 482 (s) cm . ESI-MS 293 (20 [M] ), 294 (100 [M+1] ).
Anal. calcd. for C16H15FeNO (293.14): C 65.56, H 5.16, N 4.78; found: C 65.37, H 5.03,
N 4.63.
Ferrocenyl Selenophen-2-yl Ketone (1c)
o
1
Yield: 655 mg (88%). Red solid, m.p.: 113.5–115.0 C. H NMR: δ 4.24 (s, 5H,
CH-Fc), 4.60 (t, JH,H = 1.8 Hz, 2H, CH-Fc), 5.02 (t, JH,H = 1.8 Hz, 2H, CH-Fc), 7.44 (dd,
JH,H = 5.4, 3.6 Hz, 1H, CHarom.), 8.15 (dd, JH,H = 3.6, 1.2 Hz, 1H, CHarom.), 8.35 (dd,
13
JH,H = 5.4, 1.2 Hz, 1H, CHarom.) ppm. C NMR: δ 70.4, 71.0, 72.2 (9C, CH-Fc), 78.6 (1C,
C-Fc), 130.4, 133.4, 137.8 (3C, CHarom.), 151.4 (1C, Carom.), 190.5 (1C, C=O) ppm. IR: υ
3
096 (m), 3078 (m), 1767 (w), 1710 (w), 1594 (vs, C=O), 1557 (m), 1524 (s), 1443 (s),
1422 (vs), 1376 (s), 1290 (vs), 1152 (s), 1041 (vs), 823 (s), 769 (s), 747 (s), 710 (vs), 589
−1
+
+
(
[
w), 520 (m), 498 (s), 485 (s) cm . ESI-MS 343 (45 [M] ), 344 (73 [M+1] ), 345 (100
+
+
M+2] ), 365 (58 [M+Na–1] ). Anal. calcd. for C15H12FeOSe (343.06): C 52.52, H 3.53;
found: C 52.22, H 3.51.
Synthesis of Ketone 1d
A solution of benzoic acid (2.69 mmol, 0.33 g) and TFAA (2.69 mmol, 0.37 mL) in
dry CH2Cl2 (10 mL) was stirred for ca. 2 min at room temperature. Then, TfOH (2.69 mmol,
0.16 mL) and ferrocene (2.69 mmol, 0.5 g) were added. The progress of the reaction was
monitored by TLC. The subsequent work-up procedure was analogous to the one described
for ketones 1a–c.

´
G. MLOSTON ET AL.
2
130
Ferrocenyl Phenyl Ketone (1d)
Yield: 507 mg (65%). Red solid, m.p.: 106.5 C [lit. , m.p. 106–107 C]. H NMR:
o
14
o
1
δ 4.20 (s, 5H, CH-Fc), 4.58 (t, JH,H = 1.8 Hz, 2H, CH-Fc), 4.90 (t, JH,H = 1.8 Hz, 2H,
CH-Fc), 7.46 (t, JH,H = 7.7 Hz, 2H, CHarom.), 7.54 (t, JH,H = 7.3 Hz, 1H, CHarom.), 7.89
1
3
(
d, JH,H = 7.3 Hz, 2H, CHarom.) ppm. C NMR: δ 70.2, 71.5, 72.5 (9C, CH-Fc), 78.2 (1C,
C-Fc), 128.0, 128.2, 131.4 (5C, CHarom.), 139.9 (1C, Carom.), 199.0 (1C, C=O) ppm. IR: υ
3
(
6
113 (w), 3091 (w), 3065 (w), 1626 (vs, C=O), 1597 (s), 1577 (s), 1450 (s), 1440 (s), 1375
s), 1289 (vs), 1166 (m), 1057 (m), 1025 (s), 1003 (m), 952 (m), 826 (s), 724 (vs), 696 (s),
−1
+
+
+
76 (m), 564 (m) cm . ESI-MS 290 (31 [M] ), 291 (100 [M+1] ), 313 (54 [M+Na] ).
Anal. calcd. for C17H14FeO (290.14): C 70.37, H 4.86; found: C 70.41, H 4.83.
Synthesis of Thioketones 2a–d (General Procedure)
The solution of the corresponding ketone 1 (1 mmol) in THF or benzene (5 mL)
◦
was heated to 65 C, and next LR (0.6 mmol, 0.24 g) was added. After the complete
reaction (TLC), the mixture was concentrated and the crude product was purified by flash
chromatography (hexane/CH2Cl2, 7:3).
Diferrocenyl Thioketone (2a)
◦
8
◦
Yield: 311 mg (75%). Violet solid, m.p.: >135 C (decomposition) [lit. , m.p. 135 C
1
(
decomposition)]. H NMR: δ 4.20 (s, 10H, CH-Fc), 4.68 (s, 4H, CH-Fc), 5.22 (s, 4H,
13
CH-Fc) ppm. C NMR: δ 71.3, 72.5, 72.6 (18C, CH-Fc), 90.4 (2C, C-Fc), 237.1 (1C,
C=S) ppm. IR: υ 3120 (w), 3096 (m), 3084 (m), 2958 (w), 2922 (m), 2851 (w), 1677 (m),
1
654 (m), 1623 (m), 1594 (m), 1443 (vs), 1430 (s), 1400 (m), 1378 (m), 1352 (m), 1334
(
(
(
m), 1286 (s), 1249 (vs), 1206 (m), 1190 (m), 1105 (m), 1073 (s), 1045 (s), 1004 (s), 945
m), 887 (m), 873 (m), 847 (m), 830 (s), 817 (vs), 767 (m), 696 (m), 546 (m), 516 (s), 484
vs), 474 (vs), 444 (m) cm . ESI-MS 414 (4 [M] ), 415 (100 [M+1] ), 416 (26 [M+2] ).
−1
+
+
+
Ferrocenyl N-methylpyrrol-2-yl Thioketone (2b)
◦
1
Yield: 263 mg (85%). Violet solid, m.p.: 102.0–102.8 C. H NMR: δ 3.97 (s, 3H,
CH3), 4.18 (s, 5H, CH-Fc), 4.68 (t, JH,H = 1.8 Hz, 2H, CH-Fc), 5.11 (t, JH,H = 1.8 Hz,
H, CH-Fc), 6.14 (dd, JH,H = 4.2, 2.4 Hz, 1C, CHarom.), 6.85 (dd, JH,H = 4.2, 1.8 Hz, 1C,
CHarom.), 7.72 (dd, JH,H = 2.4, 1.8 Hz, 1C, CHarom.) ppm. C NMR: δ 37.4 (CH3), 71.6,
2.8, 72.9 (9C, CH-Fc), 91.1 (1C, C-Fc), 107.6, 117.1, 132.9 (3C, CHarom.), 142.4 (1C,
Carom.), 218.0 (1C, C=S) ppm. IR: υ 3105 (m), 2948 (w), 1636 (w), 1518 (m), 1454 (s),
432 (vs), 1401 (vs), 1271 (vs), 1242 (m), 1188 (m), 1068 (s), 1048 (s), 1020 (s), 1002
2
13
7
1
−1
(
(
m), 830 (m), 821 (m), 784 (s), 742 (vs), 702 (m), 604 (m), 493 (s) cm . ESI-MS 309
54 [M] ), 310 (100 [M+1] ). Anal. calcd. for C16H15FeNS (309.21): C 62.15, H 4.89, N
+
+
4.53, S 10.37; found: C 62.36, H 4.94, N 4.53, S 10.75.
Ferrocenyl Selenophen-2-yl Thioketone (2c)
◦
1
Yield: 298 mg (83%). Green solid, m.p.: 83.5–85.0 C. H NMR: δ 4.22 (s, 5H, CH-
Fc), 4.78 (s, 2H, CH-Fc), 5.15 (s, 2H, CH-Fc), 7.45 (brs/m, 1H, CHarom.), 7.94 (brs/m, 1H,
CHarom.), 8.35 (brs/m, 1H, CHarom.) ppm. 13C NMR: δ 72.2, 73.0, 73.8 (9C, CH-Fc), 88.5

FERROCENYL THIOKETONES AND THEIR REACTIONS
2131
(
1C, C-Fc), 129.3, 131.2, 141.4 (3C, CHarom.), 162.0 (1C, Carom.), 224.9 (1C, C=S) ppm.
IR: υ 3083 (m), 1503 (m), 1432 (vs), 1410 (vs), 1379 (s), 1332 (vs), 1285 (v), 1274 (s),
1
8
228 (vs), 1214 (s), 1171 (m), 1107 (m), 1058 (s), 1042 (s), 1001 (m), 977 (m), 860 (s),
−1
30 (s), 808 (s), 716 (vs), 681 (m), 641 (m), 588 (m), 506 (s), 483 (s) cm . ESI-MS 359
+
+
(48 [M] ), 361 (100 [M+2] ). Anal. calcd. for C15H12FeSSe (359.13): C 50.17, H 3.37, S
8.93; found: C 50.25, H 3.42, S 8.97.
Ferrocenyl Phenyl Thioketone (2d)7
◦
1
Yield: 254 mg (83%). Violet solid, m.p.: 71.2–72.5 C. H NMR: δ 4.17 (s, 5H, CH-
Fc), 4.82 (s, 2H, CH-Fc), 5.05 (s, 2H, CH-Fc), 7.37 (brs/m, 2H, CHarom.), 7.47 (brs/m, 1H,
13
CHarom.), 7.67 (d, JH,H = 6.0 Hz, 2H, CHarom.) ppm. C NMR: δ 72.1, 72.6, 74.8 (9C,
CH-Fc), 89.4 (1C, C-Fc), 126.9, 127.6, 130.1 (5C, CHarom.), 149.0 (1C, Carom.), 238.7 (1C,
C=S) ppm. IR: υ 3108 (w), 3095 (w), 3073 (w), 3058 (w), 2925 (w), 2852 (w), 1592 (m),
1
1
444 (s), 1431 (vs), 1398 (m), 1374 (s), 1294 (s), 1280 (vs), 1242 (vs), 1175 (m), 1108 (m),
087 (m), 1065 (s), 1007 (vs), 932 (m), 827 (vs), 768 (vs), 701 (vs), 684 (s), 635 (m), 506
−1
+
+
+
(
vs), 483 (vs) cm . ESI-MS 230 (24 [M–Ph+1] ), 307 (100 [M+1] ), 308 (25 [M+2] ).
Anal. calcd. for C17H14FeS (306.20): C 66.68, H 4.61, S 10.47; found: C 66.82, H 4.73, S
0.42.
1
Synthesis of Thiiranes 3a–d (General Procedure)
To a solution of the appropriate thioketone 2 (1 mmol) in dry THF (4 mL) was added
a solution of diphenyldiazomethane (1 mmol, 0.19g) in dry THF (2 mL). After stirring
overnight, the reaction was completed (according to TLC). The solvent was evaporated and
the product was purified by flash chromatography (hexane/CH2Cl2, 7:3).
3,3-Diferrocenyl-2,2-diphenylthiirane (3a)
◦
1
Yield: 320 mg (55%). Orange solid, m.p.: >183 C (decomposition). H NMR: δ
3.95–3.97 (m, 2H, CH-Fc), 4.04 (s, 10H, CH-Fc), 4.09–4.10 (m, 2H, CH-Fc), 4.11–4.12
(
4
m, 2H, CH-Fc), 4.13–4.14 (m, 2H, CH-Fc), 7.09–7.13 (m, 2H, CHarom.), 7.15–7.19 (m,
H, CHarom.), 7.42 (brs, 4H, CHarom.) ppm. C NMR: δ 59.1, 72.3 (2C, Cq), 66.4, 67.4,
13
69.5, 70.7, 70.8 (18C, CH-Fc), 92.6 (2C, C-Fc), 126.5, 127.6, 130.1 (10C, CHarom.), 143.9
(2C, Carom.) ppm. IR: υ 3091 (m), 3082 (m), 3053 (w), 3026 (w), 1595 (m), 1487 (m), 1444
(m), 1412 (m), 1273 (m), 1199 (m), 1158 (m), 1106 (m), 1063 (m), 1025 (m), 1000 (m),
8
4
17 (s), 807 (s), 780 (m), 745 (m), 704 (vs), 689 (s), 633 (m), 605 (m), 571 (m), 529 (m),
−1
+
+
+
90 (vs) cm . ESI-MS 548 (100 [M–S] ), 549 (49 [M–S+1] ), 580 (79 [M] ), 581 (40
+
[
M+1] ). Anal. calcd. for C34H28Fe2S (580.34): C 70.37, H 4.86, S 5.53; found: C 70.62,
H 4.63, S 5.59.
-Ferrocenyl-2,2-diphenyl-3-(N-methylpyrrol-2-yl)thiirane (3b)
3
◦
1
Yield: 252 mg (53%). Yellow solid, m.p.: >73 C (decomposition). H NMR: δ 3.11
(s, 3H, CH3), 3.40–3.41 (m, 1H, CH-Fc), 3.81–3.82 (m, 1H, CH-Fc), 3.84–3.85 (m, 1H,
CH-Fc), 4.00–4.01 (m, 1H, CH-Fc), 4.13 (s, 5H, CH-Fc), 6.11 (dd, JH,H = 3.6, 3.0 Hz, 1H,
CHarom.), 6.25 (t, JH,H = 1.8 Hz, 1H, CHarom.), 6.60 (dd, JH,H = 3.6, 2.4 Hz, 1H, CHarom.),
6.96–7.0 (m, 2H, CHarom.), 7.02–7.08 (m, 3H, CHarom.), 7.21–7.26 (m, 5H, CHarom.) ppm.

´
G. MLOSTON ET AL.
2
132
13C NMR: δ 34.4 (1C, CH3), 57.3, 69.0 (2C, Cq), 67.3, 67.4, 69.4, 69.9, 70.8 (9C, CH-Fc),
92.1 (1C, C-Fc), 106.7, 114.3, 120.9, 126.6, 126.8, 127.0, 129.0, 132.3 (13C, CHarom.),
131.6, 139.6, 140.3 (3C, Carom.) ppm. IR: υ 3085 (w), 3057 (w), 2953 (w), 2926 (w), 1491
(
(
(
m), 1444 (m), 1307 (m), 1106 (m), 1078 (w), 1055 (w), 1030 (w), 1002 (m), 818 (m), 783
−1
+
m), 753 (m), 736 (m), 699 (s), 609 (w), 498 (m) cm . ESI-MS 443 (28 [M–S] ), 475
+
+
100 [M] ), 476 (40 [M+1] ). Anal. calcd. for C29H25FeNS (475.43): C 73.26, H 5.30, N
.95, S 6.74; found: C 73.32 H 5.41, N 3.04, S 6.69
2
3-Ferrocenyl-2,2-diphenyl-3-(selenophen-2-yl)thiirane (3c)
◦
1
Yield: 298 mg (57%). Yellow solid, m.p.: 125.0–126.7 C. H NMR: δ 3.66 (s, 1H,
CH-Fc), 3.87 (s, 1H, CH-Fc), 4.07 (s, 5H, CH-Fc), 4.09 (s, 1H, CH-Fc), 4.39 (s, 1H,
CH-Fc), 6.98–7.08 (m, 4H, CHarom.), 7.13 (brs, 3H, CHarom.), 7.19–7.27 (m, 3H, CHarom.),
13
7
.30 (d, JH,H = 6.6 Hz, 2H, CHarom.), 7.76 (d, JH,H = 4.8 Hz, 1H, CHarom.) ppm. C NMR:
δ 60.7, 72.2 (2C, Cq), 67.6, 68.2, 69.2, 70.5, 71.1 (9C, CH-Fc), 90.2 (1C, C-Fc), 126.5,
26.7, 127.2, 128.2, 129.4, 130.4, 131.1, 131.2 (13C, CHarom.), 140.4, 141.2, 151.9 (3C,
Carom.) ppm. IR: υ 3082 (m), 3055 (m), 3026 (m), 2922 (m), 2850 (m), 1598 (m), 1490 (m),
1
1
6
5
444 (m), 1227 (m), 1106 (m), 1079 (m), 1032 (m), 1001 (m), 818 (m), 777 (m), 750 (m),
−1
+
+
96 (s), 658 (m), 604 (m), 491 (m) cm . ESI-MS 524 (50 [M–1] ), 526 (100 [M+1] ),
+
27 (28 [M+2] ). Anal. calcd. for C28H22FeSSe (525.34): C 64.02, H 4.22, S 6.10; found:
C 64.09, H 4.31, S 6.11.
3-Ferrocenyl-2,2,3-triphenyl Thiirane (3d)
◦
1
Yield: 240 mg (51%). Yellow solid, m.p.: 150.2–152.2 C. H NMR: δ 3.61 (s, 1H,
CH-Fc), 3.87 (s, 2H, CH-Fc), 4.02 (s, 6H, CH-Fc), 6.90–6.93 (m, 3H, CHarom.), 7.05–7.09
(
m, 1H, CHarom.), 7.12–7.20 (m, 6H, CHarom.), 7.23–7.29 (m, 2H, CHarom.), 7.38 (brs, 2H,
13
CHarom.) ppm. C NMR: δ 64.8, 69.6 (2C, Cq), 67.8, 68.2, 68.9, 70.0, 71.2 (9C, CH-
Fc), 91.8 (1C, C-Fc), 126.2, 126.6, 126.7, 126.8, 127.0, 127.1, 129.2, 131.5, 131.7 (15C,
CHarom.), 138.9, 140.1, 140.9 (3C, Carom.) ppm. IR: υ 3081 (w), 3052 (m), 3025 (m), 2923
(
w), 2850 (w), 1597 (w), 1491 (m), 1444 (m), 1107 (m), 1078 (m), 1028 (m), 1002 (m), 816
−1
(m), 780 (m), 751 (m), 723 (m), 698 (s), 660 (m), 601 (m), 512 (m), 484 (m) cm . ESI-
+
+
+
MS 439 (24 [M–S+1] ), 472 (100 [M] ), 473 (55 [M+1] ). Anal. calcd. for C30H24FeS
472.42): C 76.27, H 5.12, S 6.79; found: C 76.26, H 4.97, S 7.18.
(
FUNDING
The authors thank the National Science Center (PL-Cracow) for financial support
within the project Maestro (Grant Maestro-3; Dec-2012/06/A/ST5/00219).
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