Synthesis and reactivity of mono-, di-, and, triiron selenocarboxylate complexes

Article abstract of DOI:10.1002/zaac.201100541

Treatment of the iron selenide (μ-Se)[CpFe(CO)₂]₂ with one equivalent of 1, 3, 5-C₆H₃(COCl)₃ gave the organoiron selenocarboxylate complex CpFe(CO)₂SeCO-3, 5-C ₆H₃(COC

Full text of DOI:10.1002/zaac.201100541

ARTICLE
DOI: 10.1002/zaac.201100541
Synthesis and Reactivity of Mono-, Di-, and, Triiron Selenocarboxylate
Complexes
Mohammad El-khateeb,*[a] Saddam Weheabby,[a] Ibrahim Jibril,[b] Helmar Görls,[c] and
Wolfgang Weigand[c]
Keywords: Iron; Complexes; Structures; Selenium; Substitution
Abstract. Treatment of the iron selenide (μ-Se)[CpFe(CO)2]2 with one
C6H3(CONH2)2 (6) complexes by reactions with NaOH or NaNH2,
equivalent of 1,3,5-C6H3(COCl)3 gave the organoiron selenocarboxyl-
respectively. The bis(seleno)-1,3-(CpFe(CO)2SeCO)2-5-C6H3(COCl)
ate complex CpFe(CO)2SeCO-3,5-C6H3(COCl)2 (1), which contains (7) and tris(seleno)-carboxylate 1,3,5-(CpFe(CO)2SeCO)3C6H3 (8)
two free acid chloride groups. Complex 1 reacted with amines, thiols, complexes were also prepared by controlled reaction of 1,3,5-
and phenols to produce the corresponding amides CpFe(CO)2SeCO- C6H3(COCl)3 with the iron selenide (μ-Se)[CpFe(CO)2]2. Complexes
3,5-C6H3(CONR2)2 (2), thioesters CpFe(CO)2SeCO-3,5-C6H3(COSR)2
(3), and aromatic esters CpFe(CO)2SeCO-3,5-C6H3(CO2Ar)2 (4), by elemental analysis as well. The X-ray structures of CpFe(CO)2-
respectively. Complex 1 was converted into the diacid CpFe(CO)2- SeCO-3,5-C6H3(COCl)2 (1) and CpFe(CO)2SeCO-3,5-C6H3-
(COSCH2Ph)2 (3b) were determined.
1–8 were characterized by spectroscopic techniques (IR, 1H-NMR) and
SeCO-3,5-C6H3(COOH)2 (5) or the diamide CpFe(CO)2SeCO-3,5-
acid chlorides gave the corresponding selenocarboxylato com-
plexes CpЈFe(CO)2SeCOR.[21] Reaction of the iron selenide
with oxalyl chloride gave the bimetallic complex [CpFe(CO)2-
SeCO]2, in which both acid chloride groups reacted with the
iron species.[22] On the other hand, the reaction with tereph-
thaloyl chloride produced either the mono- [CpFe(CO)2SeCO-
4-C6H4COCl] or the bimetallic complex {[CpFe(CO)2SeCO]2-
4-C6H4} depending on the metal-to-ligand molar ratio.[23] The
former underwent organic transformation reactions with
amines, phenols, or thiols to give the corresponding acid deriv-
atives. It was also reacted with (μ-Ex)[CpЈFe(CO)2]2 (E = S;
x = 3–5. E = Se; x = 1) to form the mixed chalcogen, mixed
CpЈ bimetallic iron complexes.[23–25]
In this work, we further investigate the interaction of the
iron selenide with tri-substituted acid chloride. Mono-, di- and
tri-selenocarboxylato iron complexes were obtained. A second
part of this work involves the transformation of the free acid
chloride groups present in the monoiron complex, CpFe(CO)2-
SeCO-3,5-C6H3(COCl)2, to other acid derivatives as amides,
esters, and thioesters.
Introduction
Monochalcogenocarboxylato metal complexes find exten-
sive applications in catalysis and industry.[1,2] They are used
as precursors for thin metal-chalcogenide films.[3,4] The chem-
istry of these complexes and their applications have been re-
viewed in journals[5,6] and advanced books as well.[7–9]
Selenocarboxylates of main group metals as well as their
transition metal analogues have been thoroughly investi-
gated.[10–13] Group 11 and 12 selenocarboxylato complexes,
with different structural types and coordination modes of the
ligand, were synthesized for single source precursors of thin
films and nanoparticles.[14–16] On the other hand, transition
metal selenocarboxylates have found application in catalysis
and electronic industry.[17,18] Cis- and trans-four coordinate
nickel, platinum, and palladium selenocarboxylates were re-
ported and structurally characterized.[19,20]
Half-sandwich iron selenocarboxylato complexes were
reported by our group. Treatment of the selenides (μ-Se)-
[CpЈFe(CO)2]2 [CpЈ = C5H5, tBuC5H4, 1,3-(tBu)2C5H3] with
* Dr. M. El-khateeb
Fax: +962-2-7201071
E-Mail: kateeb@ just.edu.jo
[a] Permanent address: Chemistry Department
Jordan University of Science and Technology
Irbid 22110, Jordan
Results and Discussion
CpFe(CO)2SeCO-3,5-C6H3(COCl)2 (1)
Present address: Faculty of Science and Arts at Alkamil
King Abdulaziz University
The reaction of the selenide complex (μ-Se)[CpFe(CO)2]2
with 1,3,5-benzenetricarboxylic acid chloride in a 1:1 metal-
to-ligand molar ratio gave the organoiron complex CpFe(CO)2-
SeCO-3,5-C6H3(COCl)2 (1), as shown in Scheme 1.
Carbonyl stretching absorptions of 1 appear as two strong
bands at 2040 and 1994 cm–1 for the two terminal carbonyl
ligands. The spectrum also shows the bands of the selenocarb-
Alkamil, 21931, Saudi Arabia
[b] Chemistry Department
Yarmouk University
Irbid, Jordan
[c] Institut für Anorganische und Analytische Chemie
Friedrich-Schiller-Universität Jena
Humboldt Straße 8
07743 Jena, Germany
Z. Anorg. Allg. Chem. 2012, 638, (᭿), 1–6
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

M. El-khateeb et al.
ARTICLE
Scheme 1.
oxylate (SeC=O: 1631 cm–1) and of the acid chloride (ClC=O: order of these carbonyl groups. The angles around the central
1
1763 cm–1). H NMR spectrum of 1 displays a singlet signal iron atom (Se–Fe–C15, Se–Fe–C16, C15–Fe–C16) are around
at δ = 5.08 ppm due to the cyclopentadienyl ligand protons. 90° showing disorder octahedral arrangement.
1
These IR and H NMR spectroscopic data are similar to those
observed for CpFe(CO)2SeCOR and CpFe(CO)2Se-4-
C6H4COCl.[21,22] The molecular structure of 1 (Figure 1)
Reactions of 1 with Nucleophiles
shows the expected iron arrangement as a piano stool with
the Cp ring as the base and the carbonyl groups and selenium
containing ligand as the legs. The Fe–C(Cp) bond lengths,
ranging between 2.071(6) to 2.091(7) Å, and Fe–C(O) bond
lengths [1.772(7), 1.780(7) Å] are within the same range ob-
served for similar systems.[21,26] The Fe–Se bond length in 1
of 2.3752(10) Å is slightly shorter than those of CpFe(CO)2-
Complex 1 has two reactive acid chloride groups, which can
be replaced by several nucleophiles facilitating the synthesis
of several tri-functional iron complexes. The reaction of 1 with
amines, thiols, or phenols gives the corresponding iron func-
tionalized complexes as shown in Scheme 1. Complexes 2–4
1
were characterized by elemental analysis, IR, and H NMR
spectroscopy, and the results are in agreement with the sug-
gested structures. The IR spectra of these complexes exhibit
two stretching frequencies in the ranges of 2026–2035 and
1980–1987 cm–1 consistent with the two terminal carbonyl
groups. These values are similar to those reported for
CpFe(CO)2SeCO-4-C6H4COY (Y = NR2, OAr, SR, OCOR)
systems.[22,23] The C=O of selenocarboxylate group appears as
a medium band in the range 1590–1629 cm–1. The spectra also
contain another ketone carbonyl frequency in the ranges of
1646–1653, 1662–1675, and 1707–1710 cm–1 for 2, 3, and 4,
respectively. These values are consistent with the inductive ef-
fect of the nitrogen, sulfur, and oxygen atoms next to the carb-
SeX complexes {X
=
SO2Ph [2.394(3) Å], CO2Et
[2.3829(8) Å], or C(S)O-4-C6H4Cl [2.3985(2) Å]}.[26–28] The
C–O bond length of the ketone carbonyl group of the seleno-
carboxylate ligand [1.218(6) Å] is very comparable to those
found in selenocarbonato complexes.[27,28] The corresponding
bond length of the free acid chloride groups are different from
each other [1.647(7), 1.187(7) Å], this difference is due to dis-
1
onyl group. The H NMR spectra of 2–4 exhibit singlet peak
for the Cp protons in the ranges of 5.00–5.05, 5.07–5.09, and
5.30–5.31 ppm, respectively. These regions reflect the elec-
tron-withdrawing ability of the amide-, thiolate-, and thioester
groups. The aromatic protons of the selenocarboxylate group
and those of the substituents (Y) are shown in the spectra with
the expected multiplicity and chemical shift regions.
The X-ray structure analysis reveals the proposed structure
of 3b as shown in Scheme 1. Its ORTEP-drawing with atomic
numbering scheme is shown in Figure 2. Selected bond lengths
and angles are given in Table 1. The structure shows that the
iron atom is in a distorted octahedral environment as indicated
from the bond angles of the iron atom, which are around 90°.
Figure 1. ORTEP drawing of CpFe(CO)2SeCO-3,5-C6H3(COCl)2 (1)
at the 50% probability level (hydrogen atoms are omitted for clarity). The Cp ring is bonded to the iron atom in a η5-fashion with
2
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–6

Mono-, Di-, and Triiron Selenocarboxylate Complexes
Fe–C bond lengths ranging from 2.061 to 2.076 Å. The Fe– at 1714 cm–1 for 6 are assigned for the stretching of the (C=O)
C(O) bond lengths are 1.750(7) and 1.762(7) Å. These Fe–C of the acid and amide moieties. The O–H and N–H frequencies
bond lengths are shorter than those reported for 1 indicating are present in the spectra at 3615 and 3122 cm–1, respectively.
stronger π back donation from iron orbital to anti-bonding CO These IR data proved the increase electron richness around the
orbital for 3b compared to 1. This suggestion is also supported central iron atom in 5 or 6 compared to that of 1. The 1H NMR
by a longer Fe–Se bond length of 3b [2.3974(10) Å] compared spectra for complexes 5 and 6 show a singlet signal due to
to that of 1. This implies that the acid chloride groups of 1 the five cyclopentadienyl ligand protons in the range 5.29–
make the selenocarboxylate moiety a better π acceptor ligand 5.31 ppm. The signal of the N–H protons of 5 is observed at
compared to the thioester substituted one. The C=O bond δ = 8.85 ppm.
lengths of the selenocarboxylate and amide functionalities are
shorter than the corresponding ones of 1.
Synthesis of 1,3-(CpFe(CO)2SeCO)2-5-C6H3COCl (7) and
1,3,5-C6H3(CpFe(CO)2SeCO)3 (8)
The reaction of the selenide complex (μ–Se)[CpFe(CO)2]2
with 1,3,5-C6H3(COCl)3 in a 2:1 or 3:1 metal-to-ligand molar
ratio gives the di- or tri-substituted iron selenocarboxylate
complexes 1,3-(CpFe(CO)2SeCO)2-5-C6H3COCl (7), 1,3,5-
(CpFe(CO)2SeCO)3C6H3 (8), and slight amount of complex 1
(Scheme 2).
Figure 2. ORTEP drawing of CpFe(CO)2SeCO-3,5-C6H3(COSCH2Ph)2
(3b) at the 50% probability level (hydrogen atoms are omitted for
clarity).
Scheme 2.
Table 1. Selected bond lengths /Å and bond angles /° of CpFe(CO)2-
3,5-C6H3(COCl)2 (1), and CpFe(CO)2-3,5-C6H3(COSCH2Ph)2 (3b).
The IR spectrum of 7 and 8 exhibit the two strong bands
for the terminal carbonyl ligands. The stretching band of the
selenocarboxylate (SeC=O) moiety appears at 1619 cm–1 and
at 1617 cm–1 for complex 7 and 8, respectively. The stretching
band (ClC=O) of the acid chloride appears at 1756 cm–1 for
1
3b
Fe–C16
Fe–C15
Fe–C14
Fe–C11
Fe–C12
Fe–C10
Fe–C13
Fe–Se
1.772(7)
1.780(7)
2.071(6)
2.083(7)
2.089(6)
1.078(7)
1.091(7)
2.3752(16)
1.891(6)
1.218(6)
Fe–C29
Fe–C30
Fe–C26
Fe–C28
Fe–C27
Fe–C24
Fe–C25
Fe–Se
1.750(7)
1.762(7)
2.061(6)
2.062(7)
2.065(6)
2.074(7)
2.076(6)
2.3974(10)
1.909(5)
1.164(6)
1
complex 7. The H-NMR spectra for complexes 7 and 8 exhi-
bit a singlet due to the five cyclopentadienyl ligand protons at
δ = 5.32 ppm and 5.30 ppm, respectively. These values are
higher than that reported for 1.
Se–C1
C1–O1
Se–C1
O1–C1
Experimental Section
C16–Fe–C15 94.8(3)
C29–Fe–C30 96.9(3)
General Comments: All experiments were done using standard
Schlenk or vacuum line techniques in a nitrogen atmosphere. Hexane,
diethyl ether, and tetrahydrofuran were dried and distilled over sodium
and benzophenone. Dichloromethane was dried and distilled over
P2O5. The selenide (μ-Se)[CpFe(CO)2]2 was synthesized according to
the literature.[21] All chemicals: [CpFe(CO)2]2, 1,3,5-benzentricarbox-
ylic acid chloride, aniline, N-methylaniline, thiophenol, α-thiophenol,
phenol, 3,5-dimethylphenol, sodium hydroxide, sodium amide, and el-
emental selenium were used as received from Acros or Aldrich. Silica
gel of particle size 0.063–0.200 mm (70–230 mesh) was employed for
column chromatography.
C16–Fe–Se
C15–Fe–Se
O1–C1–Se
C1–Se–Fe
93.0(2)
C29–Fe–Se
C30–Fe–Se
O1–C1–Se
C1–Se–Fe
88.4(2)
91.26(19)
125.5 (4)
104.27(17)
105.4(3)
121.9(4)
101.88(18)
Complex 1 was also reacted with NaOH or NaNH2 to form
the diacid CpFe(CO)2SeCO-3,5-C6H3(COOH)2 (5) or the di-
amide CpFe(CO)2SeCO-3,5-C6H3(CONH2)2 (6) (Scheme 1).
The IR spectra of 5 and 6 exhibit two strong bands (5: 2030,
1982 cm–1, 6: 2034, 1990 cm–1) due to the stretching of the
carbonyl ligands. The stretching band of the selenocarboxylate
(SeC=O) moiety for 5 appears at 1604 cm–1, which is lower
Reaction steps were monitored by thin layer chromatography (TLC):
than that of 6 (1623 cm–1). The bands at 1693 cm–1 for 5 and Merck F60 silica plates with fluorescence indicator. Infrared spectra
Z. Anorg. Allg. Chem. 2012, 1–6
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3

M. El-khateeb et al.
were recorded with a JASCO FT-IR spectrometer. 1H NMR spectra analysis C30H22FeO5SeS2 (661.43): calcd. C 54.48, H 3.35, S 9.70%;
ARTICLE
were recorded with a Bruker-Avance 400 MHz spectrometry, in deuter-
ated solvents and referenced to TMS. Elemental analyses were per-
formed with a Perkin–Elmer 240C elemental analyzer.
found: C 53.96, H 3.39, S 9.32%. IR (KBr): νCϵO 2026 (vs), 1980
1
(vs); νSC=O 1662 (s); νSeC=O 1619 (m); νC–Se 839 (w) cm–1. H NMR
(CDCl3): δ = 8.84 (d, 2 H, Ha); 8.62 (t, 1 H, Hb); 7.37 (d, 4 H, C6H5);
7.32 (t, 6 H, C6H5); 5.07 (s, 5 H, Cp); 4.35 (s, 4 H, CH2) ppm.
Preparation of CpFe(CO)2SeCO-3,5-C6H3(COCl)2 (1)
CpFe(CO)2SeCO-3,5-C6H3(CO2Ph)2 (4a): Reflux time: 3.0 h. Yield
0.20 g (64%). M.p = 205–207 °C. Color: Orange. Elemental analysis
C28H18FeO7Se (601.24): calcd. C 50.76, H 2.94%; found: C 50.06, H
3.06 %. IR (KBr): νCϵO 2035 (vs), 1986 (vs); νOC=O 1707 (s);
νSeC=O1629 (m); νC–Se 841 (w) cm–1. 1H NMR ([D6]acetone): δ = 8.96
(d, 2 H, Ha); 8.91 (t, 1 H, Hb); 7.51 (d, 4 H, C6H5); 7.39 (t, 6 H,
C6H5); 5.30 (s, 5 H, Cp) ppm.
A reddish-brown solution (0.70 g, 1.60 mmol) of (μ-Se)[CpFe(CO)2]2
in diethyl ether (50 mL) was added dropwise at room temperature to
a
solution of 1,3,5-benzenetricarboxylic acid chloride (0.43 g,
1.60 mmol) in diethyl ether (25 mL). The resulting mixture was stirred
for 3 h at room temperature. The volatiles were removed in vacuum
and the residue was re-dissolved in a minimum amount of CH2Cl2 and
transferred into a silica gel column made up in hexane. Elution with a
mixture of dichloromethane and hexane (6:4 volume ratio) gave
brown-orange band, which was collected and identified as CpFe(CO)2-
SeCO-3,5-C6H3(COCl)2, followed by a red band which was collected
and identified as CpFe(CO)2Cl. Color: Orange. Yield 0.43 g (48%),
M.p = 145–147 °C. Elemental analysis C16H8FeO5SeCl2 (485.94):
calcd. C 39.55, H 1.66%; found: C 39.57, H 1.75%. IR (CH2Cl2):
νCϵO 2040 (vs), 1994 (vs); νClC=O 1763 (vs); νSeC=O 1631 (m); νC–Se
CpFe(CO)2SeCO-3,5-C6H3(CO2-3,5-C6H3Me2)2 (4b): Reflux time:
3.0 h. Yield 0.21 g (61%), M.p = 214–216 °C. Color: Orange. Elemen-
tal analysis C32H26FeO7Se (657.35): calcd.: C 55.78, H 3.89%; found:
C 56.18, H 3.89%. IR (KBr): νCϵO 2033 (vs), 1987 (vs); νOC=O 1710
1
(s); νSeC=O 1617 (m); νC–Se 844 (w) cm–1. H NMR ([D6]acetone): δ
= 8.96 (d, 2 H, Ha); 8.93 (t, 1 H, Hb); 6.97 (br. s, 6 H, C6H3); 5.31 (s,
5 H, Cp); 2.35 (s, 12 H, CH3 ) ppm.
1
844 (m) cm–1. H NMR (CDCl3): δ = 9.07 (d, 2 H, Ha); 8.88 (t, 1 H,
CpFe(CO)2SeCO-3,5-C6H3(COOH)2 (5): Color: Brown. Reflux
time: 6.0 h. Yield 0.14 g (42%). M.p = 172–174 °C. Elemental analy-
sis C18H10FeO7Se.THF (449.05 + THF): calcd.: C 46.09, H 3.48%;
found: C 46.94, H 3.78%. IR (KBr): νCϵO 2030 (vs), 1982 (vs); νC=O
1693(s), νSeC=O 1604 (m), νC–Se 853 (w) cm–1. 1H NMR ([D6]acetone):
δ = 8.91 (d, 2 H, Ha); 8.81 (t, 1 H, Hb); 5.31 (s, 5 H, Cp) ppm.
Hb); 5.08 (s, 5 H, Cp) ppm.
Preparation of CpFe(CO)2SeCO-3,5-C6H3(COY)2 [Y =
NH(Ph) (2a), N(Me)(Ph) (2b); SPh (3a); SCH2Ph (3b);
OPh (4a); OC6H3Me2 (4b); OH (5), NH2 (6)]
CpFe(CO)2SeCO-3,5-C6H3(CONH2)2 (6): Color: Orange. Reflux
time: 2.0 h. Yield: 0.12 g (54%). M.p. 182–184 °C, Elemental analysis
C16H12FeO5SeN2.0.5CH2Cl2 (447.08 + 0.5CH2Cl2): calcd. C 40.48, H
2.68, N 5.72%; found: C 39.73, H 3.50, N 5.01%. IR (KBr): νCϵO
2034 (vs), 1990 (vs), νNC=O 1714 (vs), νSeC=O 1623 (m), νC–Se 849 (w)
A THF solution (50 mL) containing the nucleophile (1.00 mmol) and
1 (0.25 g, 0.50 mmol) in the presence of few drops of pyridine, was
heated to reflux for several hours. The volatiles were removed under
vacuum and the residue was re-dissolved in CH2Cl2 and introduced to
a silica gel column made up in hexane. Brown-orange band was eluted
with THF/hexane (2:3 volume ratio), collected, dried, and recrys-
tallized from CH2Cl2/hexane.
1
cm–1. H NMR ([D6]acetone): δ = 8.98 (m, 3 H, C6H3); 8.85 (s, 4 H,
NH2); 5.29 (s, 5 H, Cp) ppm.
CpFe(CO)2SeCO-3,5-C6H3[CONH(Ph)]2 (2a): Reflux time: 1.5 h.
Yield 0.13 g (43%). M.p = 168–170 °C. Color: Orange. Elemental
analysis C28H20FeO5SeN2·CH2Cl2 (599.27): calcd. C 50.91, H 3.24, N
4.09%; found: C 50.03, H 3.58, N 3.80. IR (KBr): νCϵO 2032 (vs),
Preparation of 1,3-(CpFe(CO)2SeCO)2-5-C6H3COCl (7)
A
solution of 1,3,5-benzenetricarboxylic acid chloride (0.25 g,
0.90 mmol) in diethyl ether (100 mL) was added slowly over a period
of 1 h to a reddish-brown solution of (μ–Se)[CpFe(CO)2]2 (1.8 mmol)
in diethyl ether (50 mL). The resulting mixture was stirred for 4 h at
room temperature. The volatiles were removed under vacuum and re-
dissolved in a minimum amount of CH2Cl2 and transferred to a silica
gel column made up in hexane. Elution with CH2Cl2/hexane (9:1 vol-
ume ratio) gave two brown-orange bands; both were collected dried
and analyzed. The first is found to be 1 and the second is 1,3-
C6H3(CpFe(CO)2-SeCO)2-5-COCl, (7), which was recrystallized from
a CH2Cl2/hexane mixture. Yield 0.15 g (23%). M.p = 163–165 °C.
Color: Brown. Elemental analysis C23H13Fe2O7Se2Cl (708.42): calcd.
C 38.88, H 2.41%; found: C 39.05, H 2.22%. IR (KBr): νCϵO 2033
1
1981 (vs); νNC=O 1653 (m); νSeC=O 1599 (m); νC–Se 845 (w) cm–1. H
NMR (CDCl3): δ = 8.73 (br. s, 2 H, Ha); 8.64 (br. s, 1 H, Hb); 8.59
(br. s, 2 H, NH); 7.69 (t, 2 H, C6H5); 7.42 (d, 4 H, C6H5); 7.21 (d, 4
H, C6H5); 5.05 (s, 5 H, Cp) ppm.
CpFe(CO)2SeCO-3,5-C6H3[CON(Me)(Ph)]2 (2b): Reflux time: 1.5
h. Yield 0.21 g (67%). M.p = 180–182 °C. Color: Orange. Elemental
analysis C30H24FeO5SeN2 (627.33 + 0.5CH2Cl2): calcd. C 54.69, H
3.76, N 4.18%; found: C 55.81, H 4.05, N 4.59%. IR (KBr): νCϵO
2031(vs), 1980 (vs); νNC=O 1646 (s); νSeC=O 1590 (m); νC–Se 845 (w)
1
cm–1. H NMR (CDCl3): δ = 7.88 (br. s, 2 H, Ha); 7.39 (br. s, 1 H,
Hb); 7.23 (d, 4 H, C6H5); 7.17 (t, 2 H, C6H5); 6.92 (d, 4 H, C6H5);
5.00 (s, 5 H, Cp); 3.42 (s, 6 H, CH3) ppm.
(vs), 1985 (vs); νClC=O 1756 (m); νSeC=O 1619 (m); νC–Se 840 (m) cm–
1
.
1H NMR ([D6]acetone): δ = 9.15 (t, 1 H, Ha); 8.84 (d, 2 H, Hb);
CpFe(CO)2SeCO-3,5-C6H3(COSPh)2 (3a): Reflux time: 4.0 h. Yield
0.24 g (73%). M.p = 120–122 °C. Color: Brown. Elemental analysis
C28H18FeO5SeS2 (633.37): calcd. C 53.10, H 2.86, S 10.13%; found:
C 53.00, H 3.01, S 9.83%. IR (KBr): νCϵO 2032 (vs), 1987 (vs); νSC=O
5.32 (s, 10 H, Cp) ppm.
Preparation of 1,3,5-C6H3(CpFe(CO)2SeCO)3 (8)
1
1675 (s); νSeC=O 1617 (m); νC–Se 835 (w) cm–1. H NMR (CDCl3): δ
A
solution of 1,3,5-benzenetricarboxylic acid chloride (0.16 g,
= 8.95 (d, 2 H, Ha); 8.69 (t, 1 H, Hb); 7.53 (m, 4 H, C6H5); 7.48 (m,
6 H, C6H5); 5.09 (s, 5 H, Cp) ppm.
0.60 mmol) in diethyl ether (25 mL) was added dropwise to a red-
brown solution of (μ-Se)[CpFe(CO)2]2 (2.0 mmol) in diethyl ether
CpFe(CO)2SeCO-3,5-C6H3(COSCH2Ph)2 (3b): Reflux time: 4.0 h. (50 mL). The resulting mixture was stirred for 4 h at room temperature.
Yield 0.22 g (65%). M.p = 132–134 °C. Color: brown. Elemental The volatiles were removed under vacuum and re-dissolved in a mini-
4
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–6

Mono-, Di-, and Triiron Selenocarboxylate Complexes
mum amount of CH2Cl2 and transferred to a silica gel column made for 3b (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
up in hexane. Elution with THF/hexane (3:7 volume ratio) gave two
brown-orange bands, both were collected dried and analyzed. The first
was a mixture of 1 and 7, the second was 1,3,5-C6H3(CpFe(CO)2-
SeCO)3 (8), which was recrystallized from CH2Cl2/hexane. Yield
0.12 g (22%), M.p = 185–187 °C. Color: Brown. Elemental analysis
C30H18Fe3O9Se3 (928.89): calcd.: C 39.28, H 2.87%; found: C 39.05,
H 2.45%. FTIR (KBr): νCϵO 2036 (vs), 1990 (vs); νSeC=O 1617 (m);
http://www.ccdc.cam.ac.uk).
Acknowledgement
This work has been funded by the Deanship of Scientific Research,
Jordan University of Science and Technology, Grant number 165/2008.
1
νC–Se 844 (w) cm–1. H NMR ([D6]acetone): δ = 8.86 (s, 3 H, C6H3);
5.30 (s, 15 H, Cp) ppm.
References
X-ray Structure Analysis of CpFe(CO)2SeCO-3,5-
C6H3(COCl)2 (1) and CpFe(CO)2SeCO-3,5-
C6H3(COSCH2Ph)2 (3b)
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1
3b
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Formula
Fw /g·mol–1
T /K
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
C16H8Cl2FeO5Se
485.93
–90(2)
triclinic
P1
7.0787(4)
12.2734(6)
20.9064(8)
84.141(3)
80.716(3)
74.732(2)
1725.89(14)
4
1.870
33.16
11387
5114
7653/0.0457
0.1291
0.0555
1.007
1.251/–1.143
NONE
C30H22FeO5S2Se
661.41
–90(2)
triclinic
¯
¯
P1
6.5279(5)
15.0929(9)
15.9657(9)
110.913(4)
101.330(5)
100.789(5)
1382.73(16)
2
1.589
20.52
9997
3300
6295/0.0496
0.1589
0.0606
0.999
0.726/–0.633
NONE
γ /°
V /Å3
Z
ρ /g·cm–3
μ /mm–1
Measured data
Data with I Ͼ 2σ(I)
Unique data (Rint
)
wR2 (all data, on F2)a)
R1 [I Ͼ 2σ(I)]a)
b)
S
Res. dens./e·Å–3
Absorpt method
a) Definition of the R indices: R1 = (Σ||Fo|–|Fc||)/Σ|Fo|; wR2
=
{Σ[w(Fo –Fc ) ]/Σ[w(Fo ) ]}1/2 with w–1 = σ2(Fo ) + (aP)2+bP; P =
Received: December 17, 2011
2
2 2
2 2
2
[2Fc + Max(Fo ]/3. b) s = {Σ[w(Fo –Fc ) ]/(No–Np)}1/2
.
Published Online: ᭿
2
2
2
2 2
Z. Anorg. Allg. Chem. 2012, 1–6
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
5

M. El-khateeb et al.
ARTICLE
M. El-khateeb,* S. Weheabby, I. Jibril, H. Görls,
W. Weigand ........................................................................ 1–7
Synthesis and Reactivity of Mono-, Di-, and, Triiron Seleno-
carboxylate Complexes
6
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–6