Alkali metal and organo group-14 element ferrocenecarboselenoates: Synthesis and structures

Article abstract of DOI:10.1002/zaac.201200368

Lithium, sodium, and potassium ferrocenecarboselenoates were synthesized in good yields by the reaction of ferrocenoyl chloride with the corresponding metal selenides. In air, the saltsquickly oxidized to give diferrocenoyl diselenide. The salts readily r

Full text of DOI:10.1002/zaac.201200368

ARTICLE
DOI: 10.1002/zaac.201200368
Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates:
Synthesis and Structures
Toshinori Takahashi,[a] Osamu Niyomura,[b] Shinzi Kato,*[b,c] and Masahiro Ebihara[a]
Keywords: Alkali metal ferrocenecarboselenoates; Selenoesters; Organotin selenoates; Organolead selenoates; X-ray diffraction
Abstract. Lithium, sodium, and potassium ferrocenecarboselenoates good yields. In contrast, the reaction of the sodium and potassium salts
were synthesized in good yields by the reaction of ferrocenoyl chloride
with the corresponding metal selenides. In air, the salts quickly oxid-
with trimethylsilyl chloride led to O-trimethylsilyl ferrocenecarbose-
lenoate FcCSeOSiMe3. Treatment of the O-silyl ester with RbF and
ized to give diferrocenoyl diselenide. The salts readily reacted with CsF led to rubidium and cesium ferrocenecarboselenoates, respec-
alkyl and organo-germanium, -tin and -lead halides to give the corre-
sponding Se-alkyl and Se-organo Group-14 element ferrocenecarbose-
lenoates [(FcCOSe)xMPh4–x (M = Ge, Sn, Pb; x = 1–3) in moderate to
tively,ingoodyields.ThestructuresofFcCOSetBu,(FcCOSe)2SnPh2,and
FcCOSePbPh3 were revealed by X-ray molecular structure analysis.
synthesis of new carbochalcogenoic acid derivatives, we de-
scribe herein the synthesis of a series of alkali metal and Se-
alkyl and Se-organo Group-14 element ferrocenecarbose-
lenoates,[5] along with the X-ray molecular structures of Se-
tert-butyl ferrocenecarboselenoate, Se-diphenyltin bis(ferro-
cenecarboselenoate), and Se-triphenyllead ferrocenecarbose-
lenoate.
Introduction
Much attention has been paid recently to the chemistry of
ferrocene derivatives, since the incorporation of a ferrocenyl
group into organic and inorganic molecules gives an easy re-
dox reaction. The synthesis of ferrocenecarbochalcogenoic
acid derivatives has been limited to ferrocenecarbothioic[1]
and -carbodithioic acid derivatives,[2] most likely due to the
difficulty of purification. To the best of our knowledge, the
synthesis of ferrocenecarboselenoic acid derivatives has been
limited to only Se-aryl ferrocencarboselenoates via the reac-
Results and Discussion
tions of ferrocenoyl chloride with areneselenolate ion prepared Synthesis
from diaryl diselenide and LiAlHSeH, diferrocenoyl selenide
Alkali Metal Ferrocenecarboselenoates
via the reaction of ferrocenoyl chloride with LiAlHSeH, and
diferrocenoyl diselenide via the reaction of ferrocenoyl chlor-
ide with LiAlHSeH, followed by I2/KI-oxidation, respec-
tively,[3] Alkali metal carbochalcogenoates M(RCEEЈ) (M = al-
kali metal; E, EЈ = O, S, Se, Te; E, EЈ ϶ O) are the most
important starting groups for the synthesis of their typical ele-
ment and transition metal derivatives, etc.
After we considered previous papers,[6] the reaction condi-
tions of ferrocenoyl chloride with alkali metal selenides were
examined for the synthesis of lithium (1), sodium (2), and po-
tassium ferrocenecarboselenoate (3) (Scheme 1). As a result,
the reactions of ferrocenoyl chloride with an excess of alkali
metal selenide in acetonitrile were found to give the corre-
sponding salts 1–3 in good yields. For example, ferrocenoyl
chloride was added dropwise to a suspension of freshly pre-
pared sodium selenide (1.5 mol amount) in acetonitrile, and the
mixture was stirred at 0 °C for 1 h. Filtration of the resulting
precipitates (excess Na2Se and NaCl) and evaporation of the
solvent under reduced pressure afforded sodium ferrocenecar-
boselenoate (2) in 80% yield as orange-brown micro crystals.
Under similar conditions, the reactions with lithium and potas-
We have developed methods for preparing a variety of alkali
metal carbochalcogenoates.[4] As part of our studies on the
* Prof. Dr. S. Kato
Fax: 81-52-222-2442
E-Mail: kshinzi@nifty.com
[a] Faculty of Engineering
Department of Chemistry
Gifu University
Gifu, Japan
[b] Department of Applied Chemistry
School of Engineering
Chubu University
Aichi, Japan
[c] Maruno-uchi 2–14–32
Lions-City Maruno-uchi 1105, Naka-ku
Nagoya 460–0002, Japan
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201200368 or from the au-
thor.
Scheme 1.
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Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates
sium selenides gave the corresponding lithium (1) and potas-
sium ferrocenecarboselenoates (3) in yields of 61% and 80%
as orange to orange-brown micro crystals, respectively
(Table 1).
Table 1. Reaction conditions and yields of lithium (1), sodium (2),
potassium (3), rubidium (4), and cesium ferrocenecarboselenoates (5).
Scheme 3.
Table 2. Synthesis of Se-alkyl ferrocenecarboselenoates 6.
On the other hand, rubidium (4) and cesium ferrocenecar-
boselenoates (5) were obtained as orange micro crystals in
moderate yields of 72% and 68%, respectively, by the reaction
of RbF and CsF with O-trimethylsilyl ferrocenecarboselenoate
(7a),[6a–6c] prepared from the reaction of the sodium 2 and po-
tassium salts 3 with trimethylsilyl chloride in acetonitrile,
respectively (Scheme 2). The structures of these salts were
No formation of Se-tert-butyl ferrocenecarboselenoate (6e)
was detected from the reaction of 3 and tert-butyl iodide at
50 °C for over 10 h, due to their bulky alkyl groups. However,
the ester 6e was obtained by the reaction of ferrocenoyl chlor-
ide with lithium or sodium tert-butylselenolate in low yield.
The rubidium 4 and cesium salts 5 appeared to be less reactive
than the salts 2 and 3, and under the same conditions they gave
Se-methyl selenoester 6a in respective yields of 67% and 57%
(entries 4, 5). A similar trend was observed for the methylation
of rubidium and cesium carbothio-.[8] and carbotelluroates.[9]
The reaction of phenacyl bromide with an electron-with-
drawing group proceeded more quickly to give the correspond-
ing Se-phenacyl selenoester (6f) in quantitative yield.
1
characterized by their IR and H, 13C, and 77Se NMR spectra
and by conversion into the corresponding Se-alkyl ferrocene-
carboselenoates (6) or Se-organo-germanium (8), -tin (9), and -
lead carboselenoates (10), or by comparison of their IR spectra
with those of authentic samples prepared by the reaction of
ferrocencarboselenoic acid with the corresponding alkali metal
hydrides or fluorides.[7]
Organo Group 14 Element Ferrocenecarboselenoates 7–10
We previously reported the reactions of alkali metal car-
bochalcogenoates [M(RCOE) (M = Li, Na, K, Rb, Cs; E = S,
Se, Te) with trimethylsilyl halides to give the corresponding O-
trimethylsilyl carbochalcogenoates [RC(=E)OSiMe3],[10] while
the reactions with organo-germanium, -tin, and -lead halides
R4–xMЈXx (MЈ = Ge, Sn, Pb) produce the E-organo Group 14
element carbochalcogenoates [(RCOE)xMЈRЈ4–x, R, RЈ = alkyl,
aryl; MЈ = Ge, Sn, Pb; E = S, Se, Te].[4a,4f]
By referring to these reaction conditions, we next examined
the reactions of potassium ferrocenecarboselenoate (3) with a
variety of organo Group-14 element chlorides (Scheme 4). The
reaction conditions and yields are shown in Table 3. For exam-
ple, when excess trimethylsilyl chloride was added to a suspen-
sion of potassium salt 3 in hexane, the color of the suspension
rapidly changed from orange to dark red. The mixture was
Scheme 2.
The salts 1–5 are orange-brown to red-brown micro crystals,
which are stable thermally and toward oxygen. For example,
when they were exposed to air at room temperature for over 2
h and below –15 °C for over one month, no appreciable change
was observed. However, the lithium 1 and sodium salts 2 are
hygroscopic (the lithium salt 1 appears to be more hygroscopic
than 2). Several attempts to obtain the water-free or solvent-
free salts under reduced pressure or by recrystallization were
unsuccessful.
Se-Alky Ferrocencarboselenoates 6
As expected, the lithium 1, sodium 2, and potassium salts 3 stirred at 23–25 °C for 1 h. Filtration of the resulting precipi-
readily reacted with primary alkyl iodides and phenacyl brom- tates and removal of the solvent under reduced pressure gave
ide at 0 °C to afford the corresponding Se-alkyl ferrocenecar- O-trimethylsilyl ferrocenecarboselenoate (7a) as a reddish pur-
boselenoates (6a, 6b, 6d) in quantitative yields (Scheme 3, ple oil. Similarly, the reaction with dimethylphenylsilyl chlor-
Table 2). The reaction with isopropyl iodide gave the expected ide led to a reddish purple oil of the corresponding O-organosi-
selenoester 6c in a low yield of 65% (entry 8).
lyl selenoester (7b).
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responding diacyl dichalcogenides in quantitative yields. In
fact, the potassium salt 3 was readily oxidized by these oxidiz-
ing agents at 0 °C to give diferrocenoyl diselenide (11) in
quantitative yield as red crystals (Scheme 5).
Scheme 5.
In general, ferrocenecarboselenoic acid derivatives, except
for Se-organyl selenoester derivatives FcCOSeR (R = alkyl,
aryl), are micro crystals or very thin plates, and are unsuitable
for X-ray crystallography. There have been only two examples
of an X-ray structure analysis for diferrocenoyl diselenide and
Se-1-(2-methylnaphthyl) ferrocenecarboselenoate.[3] After sev-
eral disappointing attempts to obtain single crystals of the fer-
rocenecarboselenoates 1–10, single crystals of Se-tert-butyl
ferrocenecarboselenoate (6e),[14] Se-diphenyltin bis(ferrocene-
carboselenoate) (9d), and Se-triphenyllead ferrocenecarbose-
lenoate (10a) were obtained from mixed solvents such as di-
ethyl ether/hexane or dichloromethane/ether/hexane. ORTEP
drawings and selected bond lengths and angles are shown in
Figure 1. Final atomic positional parameters are listed in
Table 4. Selected bond lengths, angles and torsion angles are
shown in Table 5. As shown in Figure 1(a) and Figure 2(a) in
the structure of Se-tert-butyl ferrocenecarboselenoate (6e), the
ethyl carbon atoms of the tert-butyl group, the selenocarboxyl
group, and the substituted cyclopentadienyl (hereafter called
Cp) ring plane are coplanar [Figure 1(a)]. The C(11)–O(11),
C(11)–Se(11), and C(21)–Se(11) distances are 1.207(4),
1.943(4), and 1.992(3) Å, respectively. These values indicate
C=O double and C–Se single bonds, respectively. Intermo-
lecular weak hydrogen bonding [2.649(2) Å] is observed be-
tween the carbonyl oxygen atoms and the Cp ring hydrogen
Scheme 4.
In the 13C NMR spectra, these compounds show a sharp
signal near δ = 225, which can be ascribed to their selenocarb-
onyl carbon. Moreover, the 77Se chemical shifts at δ = 887 for
7a and δ = 912 for 7b with coupling constants [J(C-Se)] of
218 Hz support the formation of a C=Se group. In addition,
treatment of these purple oils with RbF and CsF led to the
formation of rubidium 4 and cesium ferrocenecarboselenoates
5 in high yields, respectively. Under similar conditions, the
stoichiometric reactions of 3 with organo-germanium, -tin
and -lead chlorides proceeded quantitatively to afford the cor-
responding Se-organo-Group 14 element ferrocenecarbose-
lenoates 8–10 in good yields as red to red-brown crystals.
Oxidation of Alkali Metal Ferrocenecarboselenoates 1–5
leading to Diferrocenoyl Diselenide
It is well known that alkali metal and ammonium carbo- atoms (Figure S1a, Supporting Information)]. In addition,
thioates.[4,11] –selenoates,[12] and -telluroates[13a] are readily weak C···H [2.774(2) Å] (a weak CH-π-bond[15]) and H···H
oxidized by I2-KI ethanol solution or XeF2[13b] to give the cor- contacts [2.27–2.38 (1) Å] are noted between the Cp ring car-
Table 3. Synthesis of Se-organo Group-14 element ferrocenecarboselenoates 7–10.
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Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates
Figure 1. Structures of (a) Se-tert-butyl ferrocenecarboselenoate (6e), (b) Se-diphenyltin bis(ferrocenecarboselenoate) (9d), and (c) Se-tri-
phenyllead ferrocenecarboselenoate (10a). Short intramolecular contacts are shown in black dotted lines. Thermal ellipsoids are 50% propability
revel. All hydrogen atoms are omitted for clarity.
Table 4. Crystal data and data collection of FcCOSeCMe3 (6e), (FcCOSe)2SnPh2 (9d), and FcCOSePbPh3 (10a).
bon and the methyl or the cyclopentadienyl ring-hydrogen ure 1(b)]. The two C=O distances [C(11)–O(11) = 1.226(4) Å;
atoms and between the Cp ring hydrogen atoms.
C(21)–O(21) = 1.209(4) Å] are different.[16] The C=O(11)
A linear molecular chain formed by O···H hydrogen bonding ···Sn(11) and C=O(21)···Sn(11) distances are 2.744(4) Å and
is shown [Figure 2(a)]. A two-dimensional sheet is formed by 2.837(4) Å, respectively, and thus shorter than the sum of the
both short O···H hydrogen bonding and H···H contacts between van der Waals radii of oxygen and tin atoms (3.70 Å),[17] indi-
cyclopentadienyl ring-hydrogen atoms [Figure 2(b)]. A three- cating that both of the carbonyl oxygen atoms intramolecularly
dimensional arrangement is formed by the short contacts O···H contact the central tin atom. The bond angle C(31)–Sn(11)–
and H···H [Figure 2(c)].
C(41) of the two phenyl groups is 117.8(2)°. Thus, compound
In the case of diphenyltin bis(ferrocenecarboselenoate) (9d), 9d is considered to have a strained bipyramidal structure.
the two –COSe– groups, the substituted two Cp ring planes Weak hydrogen bonding is observed between the carbonyl
and the central tin atom have a nearly coplanar arrangement oxygen and Cp ring hydrogen atom, and weak CH-π-bonding
[torsion angles [Sn(11)–Se(11)–C(11)–O(11)
=
8.3(1)°; is seen between the Cp ring carbon and Cp ring hydrogen of
Sn(11)–Se(21)–C(21)–O(21) = 2.8(2)°; O(11)–C(11)–C(13)– neighboring molecules[15] (Figure S1b, Supporting Infor-
C(14) = 6.0(3); O(21)–C(21)–C(23)–C(24) = 4.5(2)°], with mation). A linear molecular chain is formed by C···H and H···H
their two C=O moieties pointing in the same direction [Fig- short contacts between the phenyl or cyclopentadienyl ring-
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T. Takahashi, O. Niyomura, S. Kato, M. Ebihara
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Figure 2. Molecular arrangements (a–c) of FcCOSeBu-t (6e). Short intermolecular contacts are shown as dotted lines. (a) One-dimensional
linear chain formed by the O···H hydrogen bonding between cyclpentadienyl ring-hydrogen and carbonyl-oxygen atoms is shown. (b) Two-
dimensional sheet formed by hydrogen bonding interactions and H···H short contacts between cyclopentadienyl ring-hydrogen atoms. (c) 3D
Network formed by stacking of these sheets.
Table 5. Selected bond distances /Å, angles /°, and torsion angles /° of FcCOSeCMe3 (6e), (FcCOSe)2SnPh2 (9d), and FcCOSePbPh3 (10a).
carbon atom and the phenyl ring-hydrogen atoms [Figure 3(a)].
On the other hand, the structure of Se-triphenyllead ferro-
A two-dimensional sheet [Figure 3(b)] and three-dimensional cenecarboselenoate (10a) shows that the –COSePb– moiety
arrangement [Figure 3(c)] are formed both by the Se···H hydro- and the substituted cyclophentadiene ring plane are nearly co-
gen bonding and by C···H and/or H···H short contacts.
planar [Figure 1(c)]. The C(11)–O(11) [1.214(2) Å] and
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Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates
Figure 3. Molecular arrangements (a–c) of (FcCOSe)2SnPh2 (10d). Dotted lines show intermolecular short contacts. (a) One-dimensional linear
chain formed by C···H and H···H short contacts between phenyl ring- or cyclopentadienyl ring-carbon atoms and phenyl ring-hydrogen atoms.
(b), Two-dimensional sheet formed by Se···H hydrogen bonding and by C···H and H···H short contacts. (c) 3D Network formed by stacking of
these sheets.
C(11)–Se(11) distances [1.941(4) Å] of the selenocarboxyl Table 6. The carbonyl stretching frequencies of the salts 1–5
group indicate a double and single bond, respectively, and the appear at 1520 cm–1, except for that of the lithium salt 1.[19]
three phenyl rings on the lead atom have a propeller-like ar- The carbonyl carbon chemical shifts appear near δ = 215,
rangement. The Pb(11)–Se(11) distance [2.629(4) Å] also indi- which reflects the slight influence of alkali metal cations. The
cates a single bond. The distance between Pb(11) and O(11) is 77Se NMR spectra were observed in the range δ = 343–361,
3.217(4) Å, which is shorter than the sum of the van der Waals and showed a tendency for downfield shifts with an increase
radii of both atoms (3.54 Å),[16] which indicates intramolecular in the atomic number of the alkali metal ions, except for the
coordination of the carbonyl oxygen to the lead atom. The lithium salt 1. These absorption bands are comparable to those
structure around the lead atom appears to be a strained trigonal of common alkali metal arenecarboselenoates [ν(C=O): 1519–
bipyramidal with one selenium, one oxygen, and three phenyl 1558 cm–1; 13C=O: δ213–222; 77Se: δ = 330–517].[6b–6e] Both
carbon atoms around the lead atom, similar to that of the sulfur the 13C (C=O) and 77Se NMR chemical shifts for Se-alkyl se-
and selenium isologues 4-MeC6H4COEPbPh3 (E = S[17]; E = lenoesters 6 show downfield shifts in the order R=C2H5, iso-
Se[18]). As expected, the carbonyl oxygen or selenium atom C3H7 and tert-C4H9, indicating hyperconjugation of the methyl
forms a weak intermolecular hydrogen bond with the benzene group. The carbonyl stretching frequencies of Se-triphenyl
ring hydrogen atom of the neighboring molecule. In addition, Group-14 element ferrocenecarboselenoates 8a, 9b, and 10a
the distances between the benzene ring carbon and hydrogen appear in the range1637–1668 cm–1 and exhibit a shift to low-
atoms of neighboring molecules are relatively short (2.813– frequency regions in going from germanium to tin and lead.
2.900 Å), indicating a weak CH-π-bond.[15] (Figure S1c, Sup- The 13C (C=O) chemical shifts, which are observed in the
porting Information). A linear molecular chain is formed by range of δ = 191–195, show a trend in downfield shifts in the
C···H and H···H short contacts between the phenyl-ring or cy- order: M = Ge, Sn, and Pb. The 77Se NMR spectra do not
clopentadienyl-carbon atom and the phenyl ring-hydrogen show a general shifting tendency.
atoms (Figure 4(a)]. The two-dimensional sheet [(Figure 4(b)]
and three-dimensional arrangement [(Figure 4(c)] are formed
by Se···H hydrogen bonding and by C···H and H···H short con-
Conclusions
tacts.
We have described the synthesis of a series of alkali metal
ferrocenecarboselenoates M(FcCOSe) (M = Li, Na, K, Rb, Cs),
which readily react with alkyl halides and organo-germa-
nium, -tin, and -lead halides at room temperature to give the
Spectra
The spectroscopic data of alkali metal ferrocenecarbose- corresponding Se-organyl FcCOSeR (R = alkyl) and Group-14
lenoates 1–5 along with those of Se-alkyl 6 and Se-triphenyl element derivatives (FcCOSe)xMPh4–x (M = Ge, Sn, Pb; x =
Group-14 element derivatives (8a, 9b, 10a) are shown in 1–2) in moderate to good yields. X-ray molecular structure
Z. Anorg. Allg. Chem. 2013, 96–107
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T. Takahashi, O. Niyomura, S. Kato, M. Ebihara
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Figure 4. Molecular arrangements (a–c) of FcCOSePbPh3 (10a). Short intermolecular contacts are shown as dotted lines. (a) One-dimensional
linear chain formed by C···H short contacts between cyclopentadienyl carbon and hydrogen atoms and by H···H short short contacts between
cyclpentadienyl ring hydrogen atoms. (b) Two-dimensional sheet formed by C···H short contacts between cyclopentadienyl ring-carbon and
phenyl ring-hydrogen atoms and H···H short contacts between phenyl and cyclopentadienyl ring hydrogen atoms. (c) 3D Network formed by
stacking of these sheets.
Table 6. Spectral data of alkali metal (1–5), Se-alkyl (6), and Se-tri-
phenyl Group-14 element ferrocenecarboselenoates (7–10).
Experimental Section
Instrumentation: The melting points were measured with a Yanagim-
oto micro melting point apparatus and uncorrected. The IR spectra
were measured with a PERKIN ELMER FT-IR 1640 and a JASCO
grating IR spectrophotometer IR-G. The 1H-NMR and 13C-NMR spec-
tra were recorded with a JNM-α400 instruments at 399.7 and
100.4 MHz, respectively with tetramethylsilane as an internal standard.
The 77Se NMR (76 MHz) spectra were obtained from a JEOL α-400
spectrometer, and 77Se chemical shifts are expressed in δ values deshi-
elded with respect to neat Me2Se as an external standard. All spectra
were acquired in the proton-decoupled mode; generally 0.05–0.3 mmol
solutions in CDCl3 (0.4 mL) were used. Electron spectra were mea-
sured with a JASCO U-Best 55. Elemental analyses were performed
by the Elemental Analysis Center of Kyoto University.
Materials: Diethyl ether was distilled from sodium/benzophenone ke-
tyl prior to use. Hexane was distilled from sodium metal. Acetonitrile
and dichloromethane were distilled from phosphorus pentoxide. Petro-
leum ether (bp: 40–60 °C) was distilled. Methanol was distilled from
magnesium powder. Lithium selenide,[6d] sodium selenide,[20] and po-
tassium selenide[20] were prepared according to the literature. Iodine,
iodomethane, -ethane, -1-methylethane and -1-butane and phenacyl
bromide, cesium fluoride, sodium metal, and tin tetrachloride were
purchased from Nacalai Tesque Inc. Dimethyltin dichloride, trimeth-
yltin chloride and triphenyltin chloride were purchased from Tokyo
Kasei Industrial Co., Ltd. Diphenyllead dichloride was purchased from
Alfa. Lithium, sodium, and potassium hydrides were purchased from
analysis revealed shortening of the C=O···Sn distances in
Wako Pure Chemical Ind. Ltd. Dimethylphenylsilyl chloride, dimeth-
ylsilyl dichloride, and trimethylsilyl chloride were purchased from
(FcCOSe)2SnPh2 as 4-MeC6H4COSeSnPh3.[18]
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Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates
Shin-Etsu Chem. Co. Ltd. Diphenylgermanium dichloride, diphenyltin
lithium hydride and conversion into Se-methyl ferrocenecarboseleno-
dichloride, ferrocenecarboxylic acid, 1.0 m hydrogen chloride/ether, ate. The IR and 13C NMR spectra were exactly consistent with those
rubidium fluoride, triphenylgermanium chloride, and triphenyllead
chloride, were purchased from Aldrich. Xenon difluoride was pur-
of the authentic compound prepared from the reactions of ferrocencar-
boselenoic acid with lithium hydride (see a part of lithium ferrocencar-
chased from Fluka. These reagents all are chemical grade and used boselenoate in the Experimental Section). IR (nujol, neat): ν˜ = 3850,
without further purification. Ferrocenoyl chloride was prepared ac- 2976, 2880, 2839, 1708, 1678, 1454 (C=O), 1424, 1376, 1330, 1232,
cording to the literature.[21] Silica gel used on column chromatography 1104, 1040, 1002, 955, 932, 872, 844, 825, 776, 673, 594, 557, 495)
was run on silica gel 60 of Kanto Chemical Co., Ltd.
cm–1. 1H NMR (CD3OD): δ = 4.18 (s, 5 H, Cp), 4.37 (s, 2 H, Cpmeta),
4.87 (s, 2 H, Cportho) ppm. 13C NMR (CD3OD): δ = 71.1 (Cp), 71.5
(Cportho), 71.8 (Cpmeta), 90.9 (Cpipso), 215.9 (COSe) ppm. 77Se NMR
(CD3OD): δ = 351.1 ppm.
X-ray Measurements: The measurement was carried out with a Ri-
gaku AFC7R four-circle diffract meter with graphite-monochromated
Mo-Kα radiation (λ = 0.71069 Å). All of the structures were solved
and refined using the teXsan crystallographic software package on an
IRIS Indigo computer. The crystals were coated with an epoxy resin
and mounted on a glass fiber. The cell dimensions were determined
from a least-squares refinement of the setting diffract-meter angles for
25 automatically centered reflections. Lorentz and polarization correc-
tions were applied to the data, and empirical absorption corrections
(ψ-scans)[22] were also applied. The structures were solved by direct
method using SHELXS-86[23] and expanded using DIRDIF92.[24] Scat-
tering factors for neutral atoms were from Cromer and Waber[25] and
anomalous dispersion[26] was used. The function minimized was
Sodium Ferrocenecarboselenoate (2). Ferrocenoyl chloride (840 mg,
3.38 mmol) was added to a suspension of sodium selenide (585 mg,
4.68 mmol) in acetonitrile (20 mL) at 0 °C in an argon atmosphere.
The color of the suspension rapidly changed from pale yellow to
orange brown. The mixture was stirred at the same temperature for 1
h. The precipitates (NaCl, excess of Na2Se and red selenium) were
filtered off. Removal of the solvent under reduced pressure (23 °C,
0.2 Torr), followed by washing the resulting residue with diethyl ether
(20 mL) gave 852 mg [80%, purity: Ͼ98% on the basis of conversion
into Se-methyl ferrocenecarboselenoate (6a)] of sodium ferrocenecar-
boselenoate (2) as orange brown micro crystals containing a small
amount of water. The IR and 13C NMR spectra were exactly consistent
with those of the authentic compound prepared from the reaction of
ferrocencarboselenoic acid with sodium hydride. IR (nujol, neat): ν˜ =
2975, 2881, 2842, 1714, 1684, 1682, 1615, 1574, 1520 (C=O), 1464,
1377, 1240, 1154, 1104, 1041, 1001, 946, 870, 837, 817, 723, 694,
Σw(|Fo|–|Fc|)2, and the weighting scheme employed was
w =
[σ2(Fo)+p2(Fo)2/4]–1. A full-matrix least-squares refinement was exe-
cuted with non-hydrogen atoms being anisotropic. The structures were
solved by direct methods using SIR97[22] and refined by using
SHELXL97.[23] The final full-matrix least-squares cycle included non-
hydrogen atoms with anisotropic thermal parameters. Hydrogen atoms
were placed in idealized positions and treated as riding atoms with
C–H distances in the range 0.93–0.98 Å.
1
550, 497) cm–1. H NMR (CD3OD): δ = 4.16 (s, 5 H, Cp), 4.34 (t, J
= 1.95 Hz, 2 H, Cpmeta), 4.86 (t, J = 1.95 Hz, 2 H, Cportho) ppm. 13C
NMR (CD3OD): δ = 71.1 (Cportho), 71.4 (Cp), 71.6 (Cpmeta), 90.9
(Cpipso), 215.7 (C=O) ppm. 77Se NMR (CD3OD): δ = 343.9 ppm.
Single Crystals of Compounds 6e, 9d, and 10a: Se-1,1-Dimethyl
ferrocenecarboselenoate (6f) (21 mg) was dissolved in diethyl ether
(0.25 mL) in a glass tube (Ø = 6 mm) and hexane (0.5 mL) was slowly
added. The glass tube with a rubber septum was allowed to stand at
room temperature (ca. 20 °C) for 2 d. Decantation of the solvents gave
red plate single crystals of 6e. Se-Diphenyltin bis(ferrocenecarbose-
lenoate) (9d) (96 mg) was dissolved in dichloromethane (2 mL). The
insoluble parts were filtered off. Diethyl ether (2 mL) and hexane
(6 mL) were slowly added to the filtrate in this order. The glass tube
with a rubber septum was allowed to stand at room temperature (ca.
20 °C) for 14 d. Decantation of the solvent gave red columnar crystals
of 9d. Se-Triphenyllead ferrocenecarboselenoate (10a) (20 mg) was
dissolved in dichloromethane (0.5 mL) and hexane (0.5 mL) was
slowly added. The tube with a rubber septum was allowed to stand at
20 °C for 12 d. Decantation of the solvents gave red plate crystals of
10a.
Potassium Ferrocenecarboselenoate (3). Ferrocenoyl chloride
(731 mg, 2.94 mmol) was added to a suspension of potassium selenide
(650 mg, 4.14 mmol) in acetonitrile (17 mL) at 0 °C in an argon atmo-
sphere. The color of the suspension rapidly changed from pale yellow
to orange brown. The mixture was stirred at the same temperature for
1 h. The brown precipitates (KCl, excess of K2Se and red selenium)
were filtered off. Removal of the solvent from the filtrate under re-
duced pressure (23 °C, 0.2 Torr), followed by washing with diethyl
ether (20 mL) gave 778 mg [80%, purity: Ͼ98% on the basis of con-
version into Se-alkyl selenoesters (6a)] of potassium ferrocenecarbose-
lenoate (3) as orange brown micro crystals. The IR spectrum was ex-
actly consistent with that of the authentic sample prepared by the reac-
tion of ferrocenecarboselenoic acid with potassium hydride.[7] IR (nu-
jol, neat): ν˜ = 2979, 2881, 2838, 1652, 1531, 1520 (C=O), 1505, 1470,
1456, 1378, 1235, 1105, 1037, 1024, 943, 813, 694, 547, 496) cm–1.
1H NMR (CD3OD): δ = 4.16 (s, 5 H, Cp), 4.33 (t, J = 1.95 Hz, 2 H,
Cpmeta), 4.84 (t, J = 1.95 Hz, 2 H, Cportho) ppm. 13C NMR (CD3OD):
δ = 71.2 (Cportho), 71.5 (Cp), 71.7 (Cpmeta), 91.1 (Cpipso), 215.7 (C=O)
ppm. 77Se NMR (CD3OD): δ = 346.2 ppm.
Alkali Metal Salts (1–5)[27]
Lithium Ferrocenecarboselenoate (1): Ferrocenoyl chloride
(700 mg, 2.80 mmol) was added to a suspension of lithium selenide
(390 mg, 4.20 mmol) in acetonitrile (20 mL). The color of the suspen-
sion rapidly changed from brown to orange brown. The mixture was Rubidium Ferrocenecarboselenoate (4). Rubidium fluoride (85 mg,
stirred at 20 °C for 1 h. Filtration of the insoluble part and removal 0.81 mmol) was added to a solution of O-trimethylsilyl ferrocenecar-
of the solvent under reduced pressure (20 °C, 0.2 Torr). Washing the boselenoate (8a) (315 mg, 0.86 mmol) in diethyl ether (10 mL) at
resulting precipitates with diethyl ether (10 mL), followed by removal 25 °C. The mixture was stirred at the same temperature for 11 h.
of the diethyl ether in vacuo gave 510 mg [61%, purity: Ͼ 90% on
Orange solid was gradually deposited. Filtration of the precipitates
the basis of conversion into Se-methyl ferrocenecarboselenoate (6a)] gave 221 mg (72%, purity: Ͼ98% on the basis of conversion into Se-
of lithium ferrocenecarboselenoate (1) as orange micro crystals the IR methyl ferrocenecarboselenoate) of rubidium ferrocenecarboselenoate
spectrum shows broad peaks at the range of 3400–3900 cm–1, indicat-
ing the presence of OH groups of water molecule. The structure was
(4) as orange microcrystalline solid. The IR and 13C NMR spectra
were exactly consistent with those of the authentic compound obtained
confirmed by comparison of the IR spectrum with that of the authentic by ferrocencarboselenoic acid with rubidium fluoride. IR (nujol, neat):
sample prepared by the reaction of ferrocenecarboselenoic acid[7] with ν˜ = 3090, 2925, 2854, 2658, 2026, 1833, 1686, 1537, 1520 (C=O),
Z. Anorg. Allg. Chem. 2013, 96–107
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
103

T. Takahashi, O. Niyomura, S. Kato, M. Ebihara
1460, 1429, 1368, 1335, 1233, 1104, 1038, 1029, 1010, 942, 854, 844, C 50.18); H 4.86 (4.81)%. IR (KBr, neat): ν˜ = 3099, 2956, 1735, 1656
ARTICLE
1
834, 813, 695, 546, 505, 486) cm–1. H NMR (CD3OD): δ = 4.18 (s,
(C=O), 1592, 1560, 1508, 1460, 1439, 1411, 1372, 1336, 1248, 1214,
5 H, Cp), 4.35 (t, J = 1.95 Hz, 2 H, Cpmeta), 4.86 (t, J = 1.95 Hz, 2 H, 1156, 1106, 1046, 1027, 1002, 943, 827, 812, 800, 678, 593, 559, 542,
1
Cportho) ppm. 13C NMR (CD3OD): δ = 71.2 (Cp), 71.5 (Cportho), 71.6
(Cpmeta), 91.0 (Cpipso), 215.2 (C=O) ppm. 77Se NMR (CD3OD): δ =
351.2 ppm.
498, 483, 474 cm–1. H NMR (CDCl3): δ = 1.47 (d, J = 7.1 Hz, 6 H,
CH3), 3.74 (hept, J = 7.0 Hz, 1 H, CH), 4.14 (s, 5 H, Cp), 4.39 (t, J
= 2.0 Hz, 2 H, Cpmeta), 4.72 (t, J = 2.0 Hz, 2 H, Cportho) ppm. 13C
NMR (CDCl3): δ = 24.6 (CH3), 32.7 (CH), 68.8 (Cportho), 70.7
(Cpmeta), 71.7 (Cp), 82.1 (Cpipso), 195.4 (C=O) ppm. 77Se NMR
(CDCl3): δ = 637.3 ppm.
Cesium Ferrocenecarboselenoate (5). A solution of freshly prepared
O-trimethylsilyl ferrocenecarboselenoate (8a) (203 mg, 0.56 mmol) in
diethyl ether (1 mL) was added to a suspension of cesium fluoride
(79 mg, 0.52 mmol) in the same solvent (4 mL) at 22 °C in an argon
atmosphere. The mixture was stirred at the same temperature for 12 h.
Orange solid was gradually deposited. Filtration of the precipitates
gave 150 mg (68%, purity: Ͼ98% on the basis of conversion into
Se-methyl ferrocenecarboselenoate) of cesium ferrocenecarboselenoate
(5) as orange micro crystals. The IR and 13C NMR spectra were ex-
actly consistent with thse of the authentic compound obtained by ferro-
cencarboselenoic acid with cesium fluoride. IR (nujol, neat): ν˜ = 2984,
2833, 1998, 1537, 1520 (C=O), 1471, 1431, 1231, 1104, 1036, 1011,
940, 891, 853, 843, 813, 723, 695, 595, 545, 504, 485) cm–1. 1H NMR
(CD3OD): δ = 4.18 (s, 5 H, Cp), 4.35 (t, J = 1.95 Hz, 2 H, Cpmeta),
4.86 (t, J = 1.95 Hz, 2 H, Cportho) ppm. 13C NMR (CD3OD): δ = 71.1
(Cp), 71.5 (Cportho, Cpmeta), 90.8 (Cpipso), 215.3 (C=O) ppm. 77Se
NMR (CD3OD): δ = 361.2 ppm.
Se-n-Butyl Ferrocenecarboselenoate (6d). Chromatographic purifi-
cation on silica gel column (developing solvent: ether/hexane = 1:5,
Rf = 0.59). Red oil. C15H18FeOSe (349.11): C 51.73 (calcd. C 51.61),
H 5.25 (5.20)%. IR (KBr, neat): ν˜ = 3098, 2958, 2930, 2872, 1668
(C=O), 1439, 1412, 1374, 1337, 1237, 1208, 1107, 1043, 1026, 1002,
940, 823, 799, 688, 545, 495) cm–1. H NMR (CDCl3): δ = 0.95 (t, J
1
= 7.4 Hz, 3 H, CH3), 1.45 (sex, J = 7.8 Hz, 2 H, CH3CH2), 1.72 (quint,
J = 7.6 Hz, 2 H, CH3CH2CH2), 3.03 (t, J = 7.3 Hz, 2 H, SeCH2), 4.22
(s, 5 H, Cp), 4.48 (t, J = 1.95 Hz, 2 H, Cpmeta), 4.83 (t, J = 1.95 Hz,
2 H, Cportho) ppm. 13C NMR (CDCl3): δ = 13.6 (CH3), 23.1
(CH3CH2), 24.7 (CH3CH2CH2), 33.0 (SeCH2), 68.9 (Cportho), 70.8,
(Cp) 71.8 (Cpmeta), 81.9 (Cpipso), 194.8 (C=O) ppm. 77Se NMR
(CDCl3): δ = 513.6 ppm.
Se-tert-Butyl Ferrocenecarboselenoate (6e). Selenium (168 mg,
2.13 mmol) was added to a pentane solution of 1.6 m tert-butyllithium
(1.3 mL, 2.08 mmol) in diethyl ether (10 mL) at 0 °C. After stirring at
the same temperature for 10 min, ferrocenoyl chloride (515 mg,
2.07 mmol) was added to the solution. The color of the solution rapidly
changed from pale yellow to orange. The mixture was stirred at the
same temperature for 1 h. The reaction mixture was extracted with
diethyl ether (35 mL). The organic layer was washed with water (ca.
30 mL for 5 times), dried with MgSO4 (ca. 2 g) for 15 min. Removal
of the solvent under reduced pressure (30 °C, 0.2 Torr), followed by
chromatographic purification of the resulting residue on silica gel
(ether/hexane = 1:5, Rf = 0.64) gave 210 mg (29%) of chemically pure
Se-tert-butyl ferrocenecarboselenoate (6e) as orange plate crystals.
Mp: 106–108 °C. C15H18FeOSe (349.11): C 51.11 (calcd. 51.61), H
5.14 (5.20)%. IR (KBr): ν˜ = 3854, 2966, 1735, 1686, 1646 (C=O),
1560, 1543, 1508, 1474, 1458, 1438, 1410, 1372, 1361, 1248, 1236,
1153, 1106, 1045, 1028, 1002, 937, 838, 821, 800, 682, 552, 522, 500,
Typical Procedure for the Synthesis of Se-alkyl 6 and Se-Group-14
Element Ferrocencarboselenoates 7–10
Se-Methyl Ferrocenecarboselenoate (6a) from Potassium Ferro-
cenecarboselenoate (3): Iodomethane (10 mL, 160 mmol) was added
to potassium ferrocenecarboselenoate (3) (395 mg, 1.19 mmol) in a
20 mL two necked round-bottomed flask at 0 °C in an argon atmo-
sphere. The mixture was stirred at the same temperature for 1 h. Di-
ethyl ether (10 mL) was added and the white precipitates (KI) were
filtered off. Removal of the solvent under reduced pressure (23 °C,
0.2 Torr) and recrystallization from a mixed solvent (35 mL) of ether/
hexane (5:30) at 0 °C gave 292.2 mg (80%, purity: Ͼ98% on the basis
of conversion into Se-methyl ferrocenecarboselenoate) of Se-methyl
ferrocenecarboselenoate (6a) as red needles. Mp: 67–69 °C.
C12H12FeOSe (307.03): C 46.92 (calcd. 46.94), H 4.10 (3.94)%. IR
(KBr, neat): ν˜ = 3852, 2359, 1774, 1652 (C=O), 1441, 1408, 1371,
1338, 1237, 1104, 1049, 1023, 1001, 945, 866, 828, 796, 679, 591,
1
486) cm–1. H NMR (CDCl3): δ = 1.59 (s, 9 H, CCH3), 4.15 (s, 5 H,
1
551, 497, 473) cm–1. H NMR (CDCl3): δ = 2.33 (s, 3 H, CH3), 4.23
Cp), 4.37 (t, J = 1.95 Hz, 2 H, Cpmeta), 4.71 (t, J = 1.95 Hz, 2 H,
Cportho) ppm. 13C NMR (CDCl3): δ = 31.7 (CCH3), 47.5 (CCH3), 68.7
(Cportho), 70.6 (Cp), 71.6 (Cpmeta), 82.6 (Cpipso), 196.7 (C=O) ppm.
77Se NMR (CDCl3): δ = 690.0 ppm.
(s, 5 H, Cp), 4.49 (t, J = 1.95 Hz, 2 H, Cpmeta), 4.84 (t, J = 1.95 Hz,
2 H, Cportho) ppm. 13C NMR (CDCl3): δ = 4.3 (1JC–Se = 59.5 Hz,
CH3), 68.8 (Cportho), 70.7 (Cp), 71.8 (Cpmeta), 81.6 (Cpipso), 194.5
(C=O) ppm. 77Se NMR (CDCl3): δ = 429.3 ppm.
Se-Phenacyl Ferrocenecarboselenoate (6f). Similar procedure to the
synthesis of compound 6d. Recrystallization solvent: a mixed solvent
(25 mL) of ether/hexane (10:15) at –20 °C for 2 d. Orange micro crys-
tals. Mp: 74–76 °C. C19H16FeO2Se (411.97): C 55.38 (calcd. 55.51),
H 4.00 (3.92)%. IR (KBr): ν˜ = 3104, 2367, 1669 (C=O), 1662 (C=O),
1596, 1560, 1446, 1408, 1374, 1277, 1250, 1104, 1054, 1032, 1008,
940, 838, 817, 803, 731, 712, 687, 606, 550, 500, 486) cm–1. 1H NMR
(CDCl3): δ = 4.16 (s, 5 H, Cp), 4.42 (s, 2 H, CH2), 4.50 (t, J = 1.95 Hz,
2 H, Cpmeta), 4.81 (t, J = 1.95 Hz, 2 H, Cportho), 7.24–8.03 (m, 5 H,
Ph) ppm. 13C NMR (CDCl3): δ = 29.4 (1JC–Se = 66.3 Hz, CH2), 68.7
(Cportho), 70.6 (Cp), 72.2 (Cpmeta), 79.9 (Cpipso), 128.3, 128.4, 133.1,
135.1 (Ph), 191.5 (1JC–Se = 139.4 Hz, SeC=O), 195.3 (C=O) ppm. 77Se
NMR (CDCl3): δ = 526.3 ppm.
Se-Ethyl Ferrocenecarboselenoate (6b): Chromatographic purifica-
tion on silica gel column (ether/hexane = 1:5, Rf = 0.64) gave 103 mg
(52%, 0.32 mmol). Red oil. C13H14FeOSe (321.06): C 48.77 (calcd.
48.63), H 4.48 (4.40)%. IR (KBr, neat): ν˜ = 3098, 2961, 2923, 2867,
2346, 1736, 1668 (C=O), 1560, 1542, 1508, 1439, 1412, 1396, 1373,
1337, 1231, 1107, 1044, 1026, 1002, 963, 939, 824, 799, 680, 546,
495 cm–1. 1H NMR (CDCl3): δ = 1.41 (t, J = 7.4 Hz, 3 H, CH3), 2.94
(q, J = 7.5 Hz, 2 H, CH2), 4.14 (s, 5 H, Cp), 4.39 (t, J = 1.95 Hz, 2
H, Cpmeta), 4.74 (t, J = 1.95 Hz, 2 H, Cportho) ppm. 13C NMR (CDCl3):
δ = 16.4 (CH3), 18.6 (1JC-Se = 57.5 Hz, CH2), 68.7 (Cportho), 70.6
(Cp), 71.7 (Cpmeta), 81.7 (Cpipso), 194.5 (C=O) ppm. 77Se NMR
(CDCl3): δ = 547.6 ppm.
Se-1-Methylethyl Ferrocenecarboselenoate (6c). Chromatographic O-Trimethylsilyl Ferrocenecarboselenoate (7a): Trimethylsilyl
purification on silica gel column (developing solvent: ether/hexane = chloride (0.15 mL, 1.2 mmol) was added to a suspension of potassium
1:5, Rf = 0.64). Red brown oil. C14H16FeOSe (335.08): C 50.39 (calcd. ferrocenecarboselenoate (3) (304 mg, 0.92 mmol) in hexane (10 mL)
104
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 96–107

Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates
at 24 °C. The mixture was stirred at the same temperature for 2 h. 327.5 ppm) ppm. 119Sn NMR (CDCl3): δ = 49.8 (1J119Sn–13C = 354,
The color of the suspension slowly changed from orange to red. The
precipitates (KCl) were filtered off. Removal of the solvent under re-
duced pressure (24 °C, 0.2 Torr) gave 259 mg (77%) of O-trimethyl-
silyl ferrocenecarboselenoate (7a) as dark red oil, which was identified
by conversion into cesium ferrocenecarboselenoate (5). IR (KBr, neat):
ν˜ = 3097, 2957, 2361, 1687, 1441, 1399, 1374, 1337, 1291, 1237,
1200, 1107, 1047, 1028, 1003, 972, 847 (C = Se), 760, 723, 675, 494)
1J119Sn–77Se = 779 Hz) ppm.
Se-Triphenyltin Ferrocenecarboselenoate (9b): Recrystallization
solvent: a mixed solvent of dichloromethane/ether/hexane (2:3:6) at
–10 °C. Red micro crystals. Mp: 146–148 °C. C29H24FeOSeSn
(643.94): C 54.10 (calcd. 54.25), H 3.85 (3.77)%. IR (KBr): ν˜ 1686,
1643 (C=O), 1560, 1543, 1508, 1479, 1458, 1430, 1244, 1107, 1074,
1041, 938, 819, 795, 730, 697, 544, 493) cm–1. H NMR (CDCl3): δ
= 4.10 (s, 5 H, Cp), 4.45 (t, J = 1.95 Hz, 2 H, Cpmeta), 4.80 (t, J =
1.95 Hz, 2 H, Cportho), 7.39–7.72 (m, 15 H, Ph) ppm. 13C NMR
(CDCl3): δ = 69.7 (Cportho), 70.7 (Cp), 72.5 (Cpmeta), 82.6 (Cpipso),
1
1
cm–1. H NMR (CDCl3): δ = 0.46 (s, 9 H, CH3), 4.09 (s, 5 H, Cp),
4.50 (t, J = 1.96 Hz, 2 H, Cpmeta), 4.90 (t, J = 1.96 Hz, 2 H, Cportho
)
ppm. 13C NMR (CDCl3): δ = 1.0 (CH3), 71.4, (Cportho) 71.5 (Cp), 73.2
1
(Cpmeta), 89.1 (Cpipso), 225.2 (C = Se, JC–Se = 218 Hz) ppm. 77Se
1
128.7, 129.6, 136.9, 138.4 (Ph), 194.3 (C = J77Se–117Sn = 854,
NMR (CDCl3): δ = 887.1 ppm.
1J77Se–119Sn = 891 Hz) ppm. 117Sn NMR (CDCl3): δ = –104.0
O-Dimethyl(phenyl)silyl Ferrocenecarboselenoate (7b): Red purple
(1J119Sn–13C 564 Hz) ppm. 77Se NMR (CDCl3):
= δ = 344.5
oil. Identification: conversion into cesium ferrocenecarboselenoate (5). (1J
IR (KBr, neat): ν˜ = 3070, 2959, 2365, 1687, 1428, 1290, 1256, 1200,
= 894 Hz) ppm.
119Sn–77Se
1
1120, 1047, 830 (C = Se), 793, 727, 700, 650, 471) cm–1. H NMR
Se-Dimethyltin Bis(ferrocenecarboselenoate) (9c): Recrystallization
solvent: a mixed solvent of dichloromethane/ether/hexane (1:2:4) at
–10 °C. Orange micro crystals. C24H24Fe2O2Se2Sn (732.77): C 39.88
(calcd. 39.34), H 3.25 (3.30)%. Mp: 185–187 °C. IR (KBr): ν˜ 1616
(C=O), 1600, 1432, 1373, 1336, 1251, 1240, 1108, 1045, 1027, 1003,
(CDCl3): δ = 0.73 (s, 6 H, CH3), 4.00 (s, 5 H, Cp), 4.45 (t, J = 1.95 Hz,
2 H, Cpmeta), 4.90 (t, J = 1.95 Hz, 2 H, Cportho), 7.26–7.64 (m, 5 H,
Ph) ppm. 13C NMR (CDCl3): δ = 2.1 (CH3), 69.7, (Cportho) 71.5 (Cp),
73.3 (Cpmeta), 89.0 (Cpipso), 128.0, 130.3, 133.0, 133.6 (Ph), 224.6 (C
940, 838, 804, 682, 546, 501, 486) cm–1. H NMR (CDCl3): δ = 1.17
1
1
= Se, JC–Se = 218 Hz) ppm. 77Se NMR (CDCl3): δ = 911.6. MS(CI)
m/z: 427 [M+ + 1]. HRMS (m/z) (EI, 20 eV): C19H20OFeSeSi:
(s, 6 H, CH3), 4.19 (s, 10 H, Cp), 4.46 (t, J = 2.0 Hz, 4 H, Cpmeta),
4.76 (t, J = 2.0 Hz, 4 H, Cportho) ppm. 13C NMR (CDCl3): δ = 3.36
(CH3), 70.6 (Cportho), 71.0 (Cp), 72.7 (Cpmeta), 82.5 (Cpipso), 199.1
(C=O) ppm. 77Se NMR (CDCl3): δ = 397.0 (1J77Se–117Sn = 690,
427.97992; calcd. 427.97981.
Se-Triphenylgermanium Ferrocenecarboselenoate (8a): Tri-
phenylgermanium chloride (149 mg, 0.44 mmol) was added to a sus-
pension of potassium ferrocenecarboselenoate (3) (147 mg, (1J119Sn–77Se = 719 Hz) ppm.
1J77Se–119Sn 726 Hz) ppm. 119Sn NMR (CDCl3): δ = –65.2
=
0.44 mmol) in diethyl ether (17 mL) at 23 °C. The mixture was stirred
Se-Diphenyltin Bis(ferrocenecarboselenoate) (9d): Diphenyltin di-
at the same temperature for 2 h. The color of the suspension slowly
changed from orange to reddish orange. Filtration of the precipitates
(KCl) and removal of the solvent under reduced pressure (23 °C,
0.2 Torr), followed by recrystallization of the resulting residue from a
mixed solvent (10 mL) of dichloromethane/ether/hexane (1:3:6) at
chloride (151 mg, 0.44 mmol) was added to a suspension of potassium
ferrocenecarboselenoate (3) (295 mg, 0.89 mmol) in dichloromethane
(12 mL) at 0 °C. The color of the suspension rapidly changed from
orange to red brown. The mixture was stirred at the same temperature
for 1 h. Filtration of the precipitates (KCl) and removal of the solvent
under reduced pressure (29 °C, 0.2 Torr), followed by recrystallization
of the resulting residue from a mixed solvent of dichloromethane/ether/
hexane (2:1:11) at –10 °C for 5 d, gave 339 mg (90%) of Se-di-
phenyltin bis(ferrocenecarboselenoate) (9d) as red micro crystals. Mp:
188–190 °C. C34H28Fe2O2Se2Sn (856.90): C 47.36 (calcd. 47.66), H
3.31 (3.29)%. IR (KBr): ν˜ 3065, 2963, 2346, 1736, 1718, 1686, 1654,
1624 (C=O), 1592, 1534, 1479, 1459, 1432, 1339, 1373, 1340, 1250,
1108, 1072, 1046, 1031, 942, 870, 797, 729, 695, 678, 548, 494, 453)
–10 °C
gave
247 mg
(94%)
of
Se-triphenylgermanium
ferrocenecarboselenoate (8a) as red plate crystals. Mp: 157–159 °C.
C29H24FeGeOSe (595.95): C 58.41 (calcd. 58.45); H 4.08 (4.06)%. IR
(KBr): ν˜ = 3651, 3630, 1719, 1680, 1661 (C=O), 1650, 1543, 1508,
1483, 1431, 1262, 1090, 1043, 1027, 792, 735, 697, 492, 456) cm–1.
1H NMR (CDCl3): δ = 4.12 (s, 5 H, Fc), 4.45 (t, J = 2.1 Hz, 2 H, Fc),
4.80 (t, J = 2.0 Hz, 2 H, Fc), 7.39–7.71 (m, 15 H, Ph) ppm. 13C NMR
(CDCl3): δ = 70.2, 70.6, 72.3, 82.8 (Fc), 128.4, 129.7, 134.9, 135.7
(Ph), 191.9 (C=O) ppm. 77Se NMR (CDCl3): δ = 352.4 ppm.
1
cm–1. H NMR (CDCl3): δ = 4.12 (s, 10 H, Cp), 4.48 (t, J = 1.95 Hz,
Se-Diphenylgermanium
Bis(ferrocenecarboselenoate)
(8b): 4 H, Cpmeta), 4.79 (t, J = 1.95 Hz, 4 H, Cportho), 7.39–7.98 (m, 10 H,
Recrystallization solvent: a mixed solvent (21 mL) of dichlorometh-
ane/hexane (1:20). Red micro crystals. Mp: 154–156 °C. IR (KBr): ν˜
= 1718, 1663 (C=O), 1484, 1435, 1397, 1372, 1338, 1246, 1106, 1089,
1042, 1003, 938, 871, 834, 819, 787, 734, 694, 676, 546, 495, 458)
Ph) ppm. 13C NMR (CDCl3): δ = 70.4 (Cportho), 70.8 (Cp), 72.7
(Cpmeta), 82.2 (Cpipso), 128.8, 129.9, 135.9, 139.2 (Ph), 196.8 (C=O)
1
ppm. 77Se NMR (CDCl3): δ = 394.2 (1J77Se–117Sn = 812, J77Se–119Sn
= 843 Hz) ppm. 119Sn NMR (CDCl3): δ = –168.9 (1J119Sn–77Se
=
1
cm–1. H NMR (CDCl3): δ = 4.12 (s, 10 H, Cp), 4.45 (t, J = 1.95 Hz,
842 Hz) ppm.
4 H, Cpmeta), 4.78 (t, J = 1.95 Hz, 4 H, Cportho), 7.41–7.94 (m, 10 H,
Ph) ppm. 13C NMR (CDCl3): δ = 70.2 (Cportho), 70.7 (Cp), 72.4
(Cpmeta), 82.1 (Cpipso), 128.4, 130.2, 134.2, 135.7 (Ph), 192.1 (C=O)
ppm. 77Se NMR (CDCl3): δ = 395.4.
Se-Phenyltin Tris(ferrocenecarboselenoate) (9e): Recrystallization
solvent: a mixed solvent of dichloromethane/hexane (4:15) at 26 °C.
Red plate crystals. Mp: 187–188 °C. C39H32Fe2O3Se3Sn (1019.76): C
46.05 (calcd. C, 46.11), H 3.25 (3.17)%. IR (KBr): ν˜ 1638 (C=O),
Se-Trimethyltin Ferrocenecarboselenoate (9a): Red micro crystals. 1431, 1371, 1244, 1106, 1041, 937, 822, 791, 732, 677, 545,
Mp: 188–190 °C. IR (KBr): ν˜ 3854, 2346, 1719, 1702, 1686, 1654,
495) cm–1. 1H NMR (CDCl3): δ = 4.28 (s, 15 H, Cp), 4.52 (t, J =
1.95 Hz, 6 H, Cpmeta), 4.86 (t, J = 1.95 Hz, 6 H, Cportho), 7.39–8.01
(m, 5 H, Ph) ppm. 13C NMR (CDCl3): δ = 70.7 (Cportho), 71.1 (Cp),
1630 (C=O), 1560, 1542, 1508, 1459, 1432, 1238, 1106, 1026, 937,
1
824, 800, 532, 498) cm–1. H NMR (CDCl3): δ = 0.54 (s, 9 H, CH3),
4.16 (s, 5 H, Cp), 4.40 (t, J = 1.95 Hz, 2 H, Cpmeta), 4.75 (t, J = 72.8 (Cpmeta), 82.0 (Cpipso), 128.9, 130.3, 134.8, 140.7 (Ph), 196.2
1.95 Hz, 2 H, Cportho) ppm. 13C NMR (CDCl3): δ = –4.2 (1J13C–117Sn (C=O) ppm. 77Se NMR (CDCl3): δ = 463.0 (1J77Se–117Sn = 1056,
1
= 339, J13C–119Sn = 354 Hz, CH3), 70.3 (Cportho), 70.7 (Cp), 72.1 1J77Se–119Sn = 1099 Hz) ppm. 119Sn NMR (CDCl3): δ = –204.1
(Cpmeta), 83.3 (Cpipso), 195.9 (C=O) ppm. 77Se NMR (CDCl3): δ =
(1J119Sn–77Se = 1104 Hz) ppm.
Z. Anorg. Allg. Chem. 2013, 96–107
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
105

T. Takahashi, O. Niyomura, S. Kato, M. Ebihara
ARTICLE
Se-Triphenyllead Ferrocenecarboselenoate (10a): Triphenyllead
chloride (282 mg, 0.60 mmol) was added to a suspension of potassium
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
ferrocenecarboselenoate (3) (199 mg, 0.60 mmol) in diethyl ether numbers CCDC-895794 (6e), CCDC-895793 (9d), and CCDC-895795
(17 mL) at 23 °C. The mixture was stirred at the same temperature for
1 h. The color of the suspension slowly changed from orange to red-
dish orange. Filtration of the precipitates (KCl) and removal of the
solvent under reduced pressure (23 °C, 0.2 Torr) and recrystallization
of the resulting residue from a mixed solvent of dichloromethane/ether/
hexane (2:2:5) at –10 °C for 2 d gave 410 mg (94%) of Se-tri-
phenyllead ferrocenecarboselenoate (10a) as red plate crystals. Mp:
144–146 °C. C29H24FeOPbSe (730.51): C 47.40 (calcd. 47.68), H 3.44
(3.31)%. IR (KBr): ν˜ 3062, 2360, 1639 (C=O), 1569, 1474, 1430,
1370, 1336, 1242, 1231, 1156, 1106, 1060, 1039, 1027, 1016, 995,
936, 862, 834, 818, 793, 726, 718, 692, 676, 542, 492, 479, 466) cm–
(10a) (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
http://www.ccdc.cam.ac.uk).
Supporting Information (see footnote on the first page of this article):
Details of the synthesis and additional figures.
Acknowledgements
This work was supported by the Grant-in-Aids for Scientific Research
(B) and on Priority Areas provided by the Ministry of Education, Sci-
ence, Sport and Culture, Japan. S·K. thanks Professor Takashi Kawa-
mura of Gifu University for the X-ray structure analysis
1
1. H NMR (CDCl3): δ = 4.10 (s, 5 H, Cp), 4.43 (t, J = 1.95 Hz, 2 H,
Cpmeta), 4.82 (t, J = 1.95 Hz, 2 H, Cportho), 7.32–7.77 (m, 15 H, Ph)
ppm. 13C NMR (CDCl3): δ = 70.6 (Cportho), 70.8 (Cp), 72.2 (Cpmeta),
83.2 (Cp ipso), 129.1, 129.8, 137.1 (Ph), 152.9 (1J13C–207Pb = 504 Hz,
References
Ph), 195.0 (C=O) ppm. 77Se NMR (CDCl3): δ = 418.6 (1J77Se–207Pb
=
[1] T. Katada, M. Nishida, S. Kato, M. Mizuta, J. Organomet. Chem.
1977, 129, 189–196.
1141 Hz) ppm.
[2] S. Kato, M. Wakamatsu, M. Mizuta, J. Organomet. Chem. 1974,
78, 405–414.
[3] S. Kumar, S. K. Tripathi, H. B. Singh, G. J. Wolmershauser, J.
Organomet. Chem. 2004, 689, 3046–3055.
Se-Diphenyllead Bis(ferrocenecarboselenoate) (10b): Recrystalli-
zation solvent: a mixed solvent of dichloromethane/hexane (6:10) at
0 °C. Red micro crystals. Mp: 160–162 °C. C34H28Fe2O2PbSe2
(945.39): C 42.80 (calcd. 43.20), H 3.09 (2.99)%. IR (KBr): ν˜ 1624
(C=O), 1567, 1474, 1434, 1371, 1339, 1245, 1108, 1045, 1028, 1013,
994, 939, 866, 817, 792, 732, 721, 690, 676, 546, 477) cm–1. 1H NMR
(CDCl3): δ = 4.12 (s, 10 H, Cp), 4.47 (t, J = 1.8 Hz, 4 H, Cpmeta), 4.82
(t, J = 1.8 Hz, 4 H, Cportho), 7.33–8.16 (m, 10 H, Ph) ppm. 13C NMR
(CDCl3): δ = 70.7 (Cportho), 70.7 (Cp), 72.4 (Cpmeta), 83.0 (Cpipso),
129.7, 130.0, 135.6, 155.0 (Ph), 198.0 (C=O) ppm. 77Se NMR
[4] a) R. Mayer, S. Scheithauer, in: Methoden der Organischen
Chemie (Ed.: J. Falbe), Georg Thieme, Stuttgart 1985; Band 5,
Teil 2, pp. 891–930; b) A. Ogawa, N. Sonoda, in: Comprehensive
Organic Functional Group Transformations, (Ed.: C. J. Moody),
Pergamon Press, Oxford, 1995, vol. 5, p. 231–255; c) A. Ishii, J.
Nakayama, in: Comprehensive Organic Functional Group Trans-
formations (Ed.: C. J. Moody), Pergamon Press, Oxford, 1995,
vol. 5, p. 505–543; d) T. Murai, S. Kato, in: Comprehensive Or-
ganic Functional Group Transformations, (Ed.: C. J. Moody),
Pergamon Press, Oxford, 1995, vol. 5, p. 545–563; e) S. Kato, T.
Murai, in Supplement B: The Chemistry of Acid Derivatives, (Ed.:
S. Patai), vol. 2, John Wiley & Sons, New York, 1992, pp. 803–
847; f) S. Kato, O. Niyomura, Top. Curr. Chem. 2005, 251, 13–
85; g) N. Kano, T. Kawashima, Top. Curr. Chem. 2005, 251, 141–
180; A. Ishii, J. Nakayama, Top. Curr. Chem. 2005, 251, 251.
[5] Oral presentation: T. Takahashi, O. Niyomura, T. Kanda, T, Mu-
rai, S. Kato, The 24th Symposium Heteroatom Chemistry, Sendai,
Japan, Abstr., p. 20, Dec. 1997; T. Takahashi, Master Thesis of
Gifu University, 1998; T. Takahashi, Bachelor Thesis of Gifu Uni-
versity, 1996.
[6] a) Y. Kawahara, S. Kato, T. Kanda, T. Murai, H. Ishihara, J.
Chem. Soc. Chem. Commun. 1993, 277–288; b) Y. Kawahara, S.
Kato, T. Kanda, T. Murai, Bull. Chem. Soc. Jpn. 1994, 67, 1881–
1885; c) Y. Kawahara, S. Kato, T. Kanda, T. Murai, J. Chem. Soc.
Chem. Commun. 1995, 87–88; d) Y. Kojima, K. Ibi, T. Kanda, H.
Ishihara, T. Murai, S. Kato, Bull. Chem. Soc. Jpn. 1993, 66, 990–
992; e) S. Kato, H. Kageyama, K. Takagi, K. Mizoguchi, T. Mu-
rai, J. Prakt. Chem. 1990, 332, 898–910.
(CDCl3): δ = 481.8 (1J77Se
–
207Pb
= 934 Hz) ppm.
Diferrocenoyl Diselenide (11)
Oxidation of the Potassium Salt 3 with I2-KI: A methanol solution
(3 mL) containing I2-KI (82 mg, 0.32 mmol) was added to a solution
of potassium ferrocenecarboselenoate (3) (188 mg, 0.57 mmol) in
methanol (10 mL) at 0 °C and the mixture was stirred for l h. Aqueous
sodium thiosulfate (ca. 5%, 20 mL) was added and extracted with
dichloromethane (25 mL). The organic layer was washed with water
(ca. 30 mLϫ5) and dried with Na2SO4 (ca. 2 g) for 15 min. Removal
of the solvent under reduced pressure (20 °C, 0.2 Torr), followed by
recrystallization from dichloromethane/hexane (1:5) at –20 °C for 4 h
gave 136 mg (87%) of compound 11 as red micro crystals. Mp: 170–
172 °C (dec.) (163–165 °C[5]) C22H18Fe2O2Se2 (583.99): C 44.68
(calcd. 44.75), H 3.05 (3.11)%. IR (KBr): ν˜ 3630, 2361, 2344, 1718,
1680 (C=O), 1654, 1560, 1542, 1508, 1459, 1431, 1367, 1262, 1239,
1
1106, 1038, 932, 822, 774, 670, 544, 492) cm–1. H NMR (CDC13):
δ = 4.32 (s, 10 H, Cp), 4.53 (t, J = 1.95 Hz, 4 H, Cpmeta), 4.88 (t, J =
1.95 Hz, 4 H, Cportho) ppm. 13C NMR (CDC13): δ = 69.7 (Cportho),
71.2 (Cp), 72.7 (Cpmeta), 785 (Cpipso), 186.7 (C=O) ppm. 77Se NMR
(CDCI3): δ = 581.7 ppm.
[7] T. Takahashi, O. Niyomura, S. Kato, M. Ebihara, Z. Anorg. Allg.
Chem. 2012, published online, DOI:10.1002/zaac.201200369.
[8] O. Niyomura, S. Kato, T. Kanda, Inorg. Chem. 1999, 38, 507–
518.
[9] S. Kato, O. Niyomura, S. Nakaiida, T. Kanda, R. Yamada, S.
Hori, Inorg. Chem. 1999, 38, 519–530.
[10] S. Kato, H. Kageyama, Y. Kawahara, T. Murai, H. Ishihara,
Chem. Ber. 1992, 125, 417–422; P. Noble Jr., D. S. Tarbell, Org.
Synth. IV 1965, 924–931.
Oxidation with XeF2: Xenon difluoride (115 mg, 0.68 mmol) was
added to a solution of potassium ferrocenecarboselenoate (3) (226 mg,
0.68 mmol) in acetonitrile (10 mL) at 0 °C and the mixture was stirred
for 10 min. The solvent was evaporated under reduced pressure.
Dichloromethane (25 mL) was added followed by stirring for 30 min.
Evaporation of the dichloromethane under reduced pressure gave
chemically pure compound 12 in 82% (153 mg).
[11] H. Adkins, Q. E. Thompson, J. Am. Chem. Soc. 1949, 71, 2242–
2244.
[12] H. Ishihara, Y. Hirabayashi, Chem. Lett. 1976, 203–206.
[13] a) T. Kakigano, T. Kanda, M. Ishida, S. Kato, Chem. Lett. 1987,
475–478; b) O. Niyomura, S. Kato, S. Inagaki, J. Am. Chem. Soc.
2000, 122, 2132–2133.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
106
www.zaac.wiley-vch.de
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2013, 96–107

Alkali Metal and Organo Group-14 Element Ferrocenecarboselenoates
[14] The compound 6f was obtained from the reaction of ferrocenoyl
chloride with lithium 1,1-dimethylselenolate (see: Experimental
Section).
[15] M. Nishio, The CH/π Interaction. Evidence, Nature and Conse-
quences, Wiley-VCH, New York, 1998; .M. Nishio, Cryst. Eng.
Commun. 2004, 6, 138–158; O. Takahashi, Y. Kohno, M. Nishio,
Chem. Rev. 2010, 110, 6049–6076.
[16] K. Tani, S. Kato, T. Kanda, S. Inagaki, Org. Lett. 2001, 3, 655–
657.
[17] A. Bondi, J. Phys. Chem. 1964, 68, 441–451.
[18] K. Tani, R. Yamada, T. Kanda, M. Suzuki, S. Kato, T. Murai,
Organometallics 2002, 21, 1487–1492.
[23] G. M. Sheldrick, in: Crystallographic Computing 3, (Eds.: G. M.
Sheldrick, C. Kruger, R. Goddard), Oxford University Press,
1985, pp.175–189.
[24] The DIRDIF-94 program system was used: P. T. Beukskens, G.
Admiraal, G. Beurskiens, W. P. Bosman, R. de Gelder, R. Israel,
J. M. M. Smits, in: Technical Report of the Crystallography Labo-
ratory; University of Nijmegen, The Netherlands, 1994.
[25] D. T. Cromer, J. T. Waber, in: International Tables for X-ray Crys-
tallography, The Kynoch Press, Birmingham, England, 1974; Vol.
IV, Table 2,2A.
[26] D. C. Creagh, W. J. McAuley, in: International Tables for X-ray
Crystallography (Ed.: A. J. C. Wilson), Kluwer Academic Pub-
lishers, Boston, 1992, Vol. C, Table 4.2.6.8, pp. 219– 222.
[27] A number of attempts to isolate and microanalyse the salts 2–5
over 10 years. However, their C, H microanalytical values were
over the allowed errors for these compounds 2, 4, and 5, though
very cross, respectively. Their high pressure mass spectroscopy
(HPMS) did not show any mother peaks. Therefore, their struc-
tures were characterized by conversion into Se-alkyl selenoesters
6. Their purities in the solid state except for compound 1, which
is extremely hygroscopic, are considered to be over 98% on the
basis of converted Se-alkyl selenoesters 6.
[19] D. R. Armstrong, A. J. Banister, J. Chem. Soc. Chem. Commun.
1986, 1672–1678.
[20] W. Klemn, H. Hodmann, P. Langmesser, Z. Anorg. Allg. Chem.
1939, 241, 281–304; F. Fehér, in: Handbook of Preparative Inor-
ganic Chemistry, (Ed.: G. Bauer), vol. I, New York, Academic
Press, 1963, p. 421.
[21] D. Seyferth, H. P. Hofmann, R. Burton, J. F. Helling, Inorg.
Chem. 1962, 1, 227–231; T. Ito, N. Sugihara, Y. Kindaichi, Y.
Takami, Nippon Kagaku Kaishi 1976, 353–355 (Chem. Abstr.
1976, 85, 7661).
[22] A. C. T. North, D. C. Phillips, F. S. Mathews, Acta Crystallogr.,
Received: August 15, 2012
Sect. A 1968, 24, 351–359.
Published Online: December 18, 2012
Z. Anorg. Allg. Chem. 2013, 96–107
© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
107