Synthesis and characterization of cyclopentadienyltricarbonyl tungsten selenocarboxylate and selenosulfonate complexes

Article abstract of DOI:10.1016/j.ica.2006.06.019

Cyclopentadienyltricarbonyl tungsten selenocarboxylate complexes CpW(CO)₃SeCOR (1) (R = C₆H₅ (a), 3,5-C₆H₃(NO₂)₂ (b), 3-C₆H₄NO₂ (c), 4-C₆H₄NO₂ (d), CH₃ (e)) and cyclopentadienyltricarbonyl tungsten selenosulfonate complexes CpW(CO)₃SeSO₂R (2) (R = C₆H₅ (a), 4-C₆H₄CH₃ (b), 4-C₆H₄OCH₃ (c), 4-C₆H₄Cl (d), CH₃ (e)) have been prepared from the tungsten anion [CpW(CO)₃Se]^- and acid- or sulfonyl chlorides respectively. The new complexes (1 and 2) have been characterized by IR, ¹H NMR spectroscopies as well as elemental analysis. The crystal structure of CpW(CO)₃SeCO-3-C₆H₄NO₂ (1c) was determined.

Full text of DOI:10.1016/j.ica.2006.06.019

Inorganica Chimica Acta 359 (2006) 4259–4264
www.elsevier.com/locate/ica
Synthesis and characterization of cyclopentadienyltricarbonyl tungsten
selenocarboxylate and selenosulfonate complexes
a,
a
a
b
Mohammad El-khateeb *, Khalil Asali , Tariq Abu Salem , Richard Welter
a
Chemistry Department, Jordan University of Science and Technology, Irbid 22110, Jordan
Laboratoire DECMET, ILB Universite´ Louis Pasteur, 4, rue Blaise Pascal 67000 Strasbourg, France
b
Received 4 January 2006; received in revised form 5 June 2006; accepted 11 June 2006
Available online 20 June 2006
Abstract
Cyclopentadienyltricarbonyl tungsten selenocarboxylate complexes CpW(CO)3SeCOR (1) (R = C6H5 (a), 3,5-C6H3(NO2)2 (b), 3-
C6H4NO2 (c), 4-C6H4NO2 (d), CH3 (e)) and cyclopentadienyltricarbonyl tungsten selenosulfonate complexes CpW(CO)3SeSO2R (2)
(R = C6H5 (a), 4-C6H4CH3 (b), 4-C6H4OCH3 (c), 4-C6H4Cl (d), CH3 (e)) have been prepared from the tungsten anion [CpW(CO)3Se]ꢀ
and acid- or sulfonyl chlorides respectively. The new complexes (1 and 2) have been characterized by IR, 1H NMR spectroscopies as well
as elemental analysis. The crystal structure of CpW(CO)3SeCO-3-C6H4NO2 (1c) was determined.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Tungsten; Selenium; Selenocarboxylate; Selenosulfonate; Complexes; Structure
1. Introduction
reaction of [Cp0Cr(CO)3]2 (Cp0 = C5H4Me, C5H4COMe,
C5H4COEt, C5H4CO2Me) with one equivalent of selenium
produced the linear selenide complexes (l-Se)[Cp0Cr(CO)2]2
which contain a Cr–Se triple bond. The later complexes
could be converted to the butterfly complexes, (l-Se2)-
[Cp0Cr(CO)2]2 upon treatment with another equivalent of
selenium [17,18]. It has been reported that upon heating
under reflux of the dimmers [Cp0M(CO)2]2 (Cp0 = C5H5,
C5H4But, C5H3(But)2) with elemental selenium gave com-
plexes of the type (l-Sex)[Cp0M(CO)2]2 (M = Fe; x = 1,
M = Ru, x = 5) [19–21]. The selenides of molybdenum and
tungsten (l-Sex)[Cp*M(CO)3]2 (M = Mo, W; Cp* =
C5Me5; x = 3, 4) have been prepared from the insertion of
elemental selenium into the M–M bond of the corresponding
dimers [22]. However, the unsubstituted Cp-analogue of
tungsten is prepared by reaction of the anion [CpW(CO)3]ꢀ
with elemental selenium followed by treatment with silica gel
[23].
The synthesis of metal complexes containing selenium
ligands is driven by their potential application in industry
[1–7], catalysis [8–10] and biological systems [11–16]. These
complexes have been tested to produce binary metal-sele-
nides that find potential utility in the fabrication of new
electronic devices such as semiconductors, super conduc-
tors and photo-conducting materials [1–7]. Selenium has
been found in a surprising number of proteins and enzymes
such as dehydrogenase and glutathione peroxidase [11].
Spectroscopic and X-ray absorption studies indicate that
the metal–selenium interaction is the active site of the
[Fe–Ni–Se] hydrogenase which contains a unique Ni–sele-
nocysteine interaction [13–16].
One convenient selenium source for the preparation of
organometallic compounds of selenium is elemental sele-
nium. It is capable of insertion into the metal–metal bonds
of organometallic dimers. Accordingly, several examples of
such insertions are reported in the literature [14–18]. The
Organotungsten–selenolate chemistry has been investi-
gated by Tho¨ne et al. The nucleophilic attach of tungsten
anion, CpWðCOÞ3ꢀ, to selenium and subsequent reaction
with organohalides gives CpW(CO)3SeR (R = allyl, ben-
zyl) [24,25]. The later complexes react with M(CO)5THF
*
Corresponding author. Tel.: +962 2 7201000; fax: +962 2 7095014.
E-mail address: kateeb@just.edu.jo (M. El-khateeb).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.06.019

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M. El-khateeb et al. / Inorganica Chimica Acta 359 (2006) 4259–4264
(M = Mo, W), Ph3PAu+, or CpFeðCOÞ
to form the
oxylate complexes are stable complexes as solids, but they
are air sensitive in solution. They are soluble in most polar
organic solvents such as CH2Cl2, Et2O, THF, but are
insoluble in nonpolar hydrocarbon solvents. The phenylse-
lenocarboxylate complex 1a was previously reported [31].
Complexes 1 were characterized on the bases of their IR,
1H NMR spectra and their elemental analysis. The IR-
spectra for compounds 1 in the carbonyl stretching region
exhibited three intensive bands in the ranges 2038–2032,
1962–1955, and 1942–1935 cmꢀ1 corresponding to the
stretching bands of the terminal carbonyl ligands bonded
to the tungsten atom. These stretching frequencies are
lower than those of the complex CpW(CO)3Cl (2053 and
1968 cmꢀ1) [32] but higher than those of CpW(CO)3SeR
(2018–2020 and 1925–1921 cmꢀ1) [24,25]. This difference
implies that the selenocarboxylate ligand is stronger p-
acceptor than –SeR ligand. The stretching frequency of
the ketonic CO-group of the selenocarboxylate ligand
appears in the range (1663–1616 cmꢀ1), comparable to
those in metal complexes containing selenocarboxylate
ligands [19].
ꢀ
2
bimetallic complexes CpW(CO)3(l-SeR)M(CO)5, CpW-
(CO)3(l-SeR)Au(PPh3), or CpW(CO)3(l-SeR)FeCp(CO)2,
respectively [26]. The use of di- or tetra-halides in the reac-
tion with the anion [CpW(CO)3Se]ꢀ led to the formation of
homonuclear dimers of the forms (C6H4)[CH2SeWCp-
(CO)3]2 and (C6H5CH)[(SeWCp(CO)3)]2 [27].
In the last few years we have synthesized several series of
iron–selenium complexes by reacting the iron selenide
(l-Se)[CpFe(CO)2]2 with electrophiles [19,28–30]. The reac-
tions of this selenide with acid chlorides [19], sulfonyl chlo-
rides [28] or chloroformates [30] were found to give the
corresponding selenocarboxylate, selenosulfonate or sele-
nocarbonate complexes, respectively. The photolytic reac-
tion of the selenocarboxylates with EPh3 (E = P, As, Sb)
gave exclusively the mono substituted complexes CpFe
(CO)(EPh3)SeCOR [29].
As part of our interest in the field of organometallic
complexes with selenium ligands and the availability of
the anion, [CpW(CO)3Se]ꢀ [25], we hereby report the syn-
thesis and characterization of tungsten selenocarboxylate
and selenosulfonate complexes.
The 1H NMR spectra of compounds 1 show a sharp res-
onance for the g5-cyclopentadienyl protons in the range of
5.77–5.24 ppm, while the protons of the selenocarboxylate
group are shown in the expected regions with the expected
multiplicity. Chemical shifts for the Cp-protons of 1 are
similar to that of CpW(CO)3Cl (5.75 ppm) [32], and higher
than that of CpW(CO)3SeCH2Ph (5.22 ppm) [25]. The lat-
ter difference may be attributed to the relatively lower elec-
tron density around the tungsten atom in complexes 1
compared to the selenolate analogues.
2. Results and discussion
A solution of the anion [CpW(CO)3Se]ꢀ (generated as
shown in Scheme 1) reacts with acid chlorides at room
temperature to give the corresponding selenocarboxylate
complexes, CpW(CO)3SeCOR (1) (R = C6H5 (a), 3,5-
C6H3(NO2)2 (b), 3-C6H4NO2 (c) 4-C6H4NO2 (d) CH3 (e))
(Scheme 1). A side product, CpW(CO)3Cl was also
obtained during these reactions. The two products were
separated by column chromatography. These selenocarb-
The molecular structure of CpW(CO)3SeCO-3-
C6H4NO2, 1c is shown in Fig. 1. Bond distances and
W(CO)6
Na
+
THF
Na
Se
W
W
Na+
Se-
CO
OC
OC
OC
CO
OC
RSO2Cl
RCOCl
O
O
O
W
W
S
OC
OC
Se
R
Se
R
OC
OC
CO
CO
2
1
R= C6H5 (a), 3,5-C6H3(NO2)2 (b),
3-C6H4NO2 (c), 4-C6H4NO2 (d), CH3 (e)
R= C6H5 (a), 4-C6H3CH3 (b),
4-C6H4OCH3(c), 4-C6H4Cl (d), CH3 (e)
Scheme 1.

M. El-khateeb et al. / Inorganica Chimica Acta 359 (2006) 4259–4264
4261
Fig. 1. ORTEP drawing of CpW(CO)3SeCO-3-C6H4NO2 (1c)
selected bond angles of 1c are shown in Table 1. The com-
plex consists of discrete monomeric molecule in which the
ring is bonded to the W atom in g5-fasion with W–C bond
was also obtained as a side product as was observed during
the preparation of 1, vide supra. Complexes 2 are stable as
solids, but they are air sensitive in solution. They are solu-
ble in most organic solvents such as CH2Cl2, Et2O, THF,
but are slightly soluble in hydrocarbon solvents.
˚
distances ranging between 2.295 (8) to 2.382 (7) A. The
˚
compound has a W–Se bond length of 2.6286 (9) A which
is similar to that observed in CpW(CO)3SeCH2-
The IR spectra of compounds 2 exhibit three strong
bands in the ranges 2042–2036 cmꢀ1, 2024–2019 and
1940–1936 cmꢀ1 corresponding to the stretching band of
the terminal carbonyl ligands bonded to the tungsten atom.
These stretching frequencies are higher than those for
CpW(CO)3SeR (2020 and 1925–1922 cmꢀ1) [25,26]. Com-
paring the stretching frequencies of compounds 2 to those
of compounds 1, one can see that those for 2 are higher
than those for 1. From these results it can be concluded
that selenosulfonate ligand is stronger p-acceptor than sel-
enolate and selenocarboxylate ligands. The spectra are also
show two medium bands in the ranges of 1264–1261 and
1148–1134 cmꢀ1, for the asymmetric and the symmetric
SO vibrations. These stretching frequencies are within the
range observed for reported selenosulfonate metal com-
plexes [33,34].
˚
C(CH3)@CH2 (2.63 (2) A) [26]. The Se–CO bond length
˚
(1.920 (7) A) is slightly shorter than the corresponding
Se–C bond in CpW(CO)3SeCH2C(CH3)@CH2 (1.985
˚
(12) A) [26], and also slightly shorter than corresponding
˚
Se–C bond in CpW(CO)3SeCH2Ph (1.961 (11) A) [25].
The C–O bond length of selenocarboxylate is (1.216
˚
(10) A) which is comparable to this in CpFe(CO)2SeCO2Et
˚
(1.192 (5) A) [30]. The coordination around the W atom of
the cyclopentadinyl ring (taken as bound at is centroid) the
three C atoms of the three CO ligands and the Se atom of
selenocarboxylate moiety can be described as a four legged
piano stole, the values of C1–W–C3, C2–W–C3, C1–W–
C2, and C2–W–Se angles involving the legs are 106.5(3)ꢁ,
76.7(3)ꢁ, 74.8(3)ꢁ, 134.5(3)ꢁ respectively.
A series of new tungsten selenosulfonato derivatives
CpW(CO)3SeSO2R (2) R = C6H5 (a), 4-C6H4CH3 (b), 4-
C6H4OCH3 (c), 4-C6H4Cl (d), CH3 (e)) have been prepared
as shown in Scheme 1. During this syntheses, CpW(CO)3Cl
1
The H NMR spectra of compounds 2 show a singlet
peak due to the cyclopentadinyl ligand protons in the range
6.26–6.13 ppm. This peak is higher in frequency compared
to the peak for CpW(CO)3SeCH2Ph (5.22 ppm) [26], and
also higher than the peak for complexes 1 (5.77–
5.24 ppm). This may due to the lower electron density
around the tungsten atom in complexes 2.
Table 1
˚
Selected bond length (A) and selected bond angles (ꢁ) of CpW(CO)3SeCO-
3-C6H4NO2 (1c)
The low yields reported for the preparation of 1 and 2 is
calculated upon the starting hexacarbonyl. This yield is the
overall yield of all steps shown in Scheme 1. No attempts to
isolate any of the intermediates have been attempted.
W–C1
W–C2
W–C6
W–C5
W–C4
W–Se
1.985(8)
1.985(8)
2.295(8)
2.325(8)
2.382(7)
2.6286(9)
C3–O3
W–C3
W–C7
W–C8
O4–C9
Se–C9
1.138(10)
2.009(7)
2.301(8)
2.364(8)
1.216(10)
1.920(7)
3. Experimental
C1–W–C2
C5–C4–W
C2–W–C7
C2–W–C5
C1–W–C8
C1–W–Se
C3–W–Se
C5–W–Se
C9–Se–W
74.8(3)
70.4(4)
84.7(3)
126.3(3)
159.8(3)
76.7(2)
78.3(2)
93.5(2)
102.5(2)
C2–W–C3
C6–C7–W
C8–C4–W
O3–C3–W
C5–C6–W
O5–N–O6
O5–N–C15
C14–C10–C11
76.7(3)
71.8(5)
71.4(4)
178.9(8)
73.6(5)
123.3(7)
118.9(6)
119.5(6)
All reactions have been performed with standard
Schlenk line techniques under dinitrogen atmosphere. Tet-
rahydrofuran (THF), hexane, and diethylether (Et2O)
were dried and distilled over sodium/benzophenone.
Dichloromethane (CH2Cl2) was dried and distilled over
P2O5. The reagents: W(CO)6, sulfonyl chlorides, acid
chlorides and gray selenium were obtained from commer-

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M. El-khateeb et al. / Inorganica Chimica Acta 359 (2006) 4259–4264
1
cial sources and used without further purification. Silica
gel of particle size 0.063–0.200 mm (70–230 mesh ASTM)
was employed for column chromatography. All reaction
steps were followed by thin layer chromatography
(TLC). Infrared spectra were recorded on a Nikolet-
Impact 410 FT-IR spectrometer in CHCl3. 1H NMR
spectra were recorded using a 200 MHz Bruker or
400 MHz Mercury-400BB ‘‘SchilfSUN’’ spectrometer.
Chemical shifts are reported in ppm downfield of TMS
and referenced using the chemical shifts of residual sol-
vent resonance. Elemental analyses were performed by
(s); mC@O 1635 (w); mNO 1544 (m), 1344 (m). H NMR
2
(CDCl3): d 5.77 (s, 5H, C5H5); 9.18 (t, 1H, C6H3); 9.24
(d, 2H, C6H3). Anal. Calc. for C15H8WO8N2Se: C, 29.68;
H, 1.33. Found: C, 29.73; H, 1.23%.
3.1.3. CpW(CO)3SeCO-3-C6H4NO2 (1c)
Brown crystals (0.34 g, 21%). m.p. = 162–164 ꢁC. IR
(CHCl3, cmꢀ1): mC”O 2035 (s), 1959 (s), 1939 (s); mC@O
1
1616 (w); mNO 1537 (m), 1351 (m). H NMR (CDCl3): d
2
5.75 (s, 5H, C5H5); 7.60 (m, 1H, C6H4); 8.38 (m, 1H,
C6H4); 8.45 (m, 1H, C6H4); 8.94 (m, 1H, C6H4). Anal. Calc.
for C15H9WO6NSe: C, 32.06; H, 1.61. Found: C, 32.11; H,
1.75%.
´
´
laboratoire D’Analyse Montreal (University of Montreal)
Canada. Melting points were recorded by SMP3 melting
point apparatus and were uncorrected.
3.1.4. CpW(CO)3SeCO-4-C6H4NO2 (1d)
Brown crystals (0.41 g, 26%). m.p. = 186–188 ꢁC. IR
3.1. General procedure for the preparation of
CpW(CO)3SeCOR (1)
(CHCl3, cmꢀ1): mC”O 2035 (s), 1959 (s), 1935 (s); mC@O
1
1636 (w); mNO 1526 (m), 1347 (m). H NMR (CDCl3): d
2
In a 100-mL Schlenk flask fitted with a reflux con-
denser, 0.10 g sodium (4.35 mmol) was dispersed by rapid
stirring in 20 mL of refluxing toluene. After stirring was
stopped, the suspension was cooled to ambient tempera-
ture and toluene was removed by syringe. The sodium
sand obtained was washed with 20 mL of THF, followed
by addition of 20 mL of THF to the sodium sand. Freshly
distilled cyclopentadiene 0.60 mL (9.74 mmol) was added
dropwise to the sodium suspension at room temperature.
When all sodium was dissolved, a dark red solution of
sodium cyclopentadienide was formed. To the resulting
solution, 0.98 g (2.78 mmol) of W(CO)6 was added and
the solution was refluxed until no W(CO)6 found in the
solution by giving dark red-brown solution of
CpW(CO)3Na. Gray selenium 0.22 g (2.78 mmol) was
added to the solution and the solution was stirred for
1 h. Acid chloride (2.78 mmol) was added to the solution
and stirred over night. The solution was filtered over Cel-
ite and the solvent was removed under vacuum and redis-
solved in a minimum amount of methylene chloride
(CH2Cl2) and was introduced to a silica gel column made
up in hexane. Elution with hexane eliminated the excess
acid chloride, and with CH2Cl2 gave an orange band
which was collected and identified as CpW(CO)3Cl, fol-
lowed by a red band which was also collected and identi-
fied as CpW(CO)3SeCOR. The CpW(CO)3SeCOR (1)
complexes were recrystallized from CH2Cl2/hexane.
5.74 (s, 5H, C5H5); 7.98 (d, 2H, C6H4); 8.28 (d, 2H,
C6H4). Anal. Calc. for C15H9WO6NSe: C, 32.06; H, 1.61.
Found: C, 32.71; H, 1.62%.
3.1.5. CpW(CO)3SeCOCH3 (1e)
Yellow crystals (0.22 g, 17%). m.p. = 86–88 ꢁC. IR
(CHCl3, cmꢀ1): mC”O 2032 (s), 1955 (s), 1935 (s); mC@O
1
1663 (w). H NMR (CDCl3): d 2.51 (s, 3H, CH3); 5.24 (s,
5H, C5H5); Anal. Calc. for C10H8WO4Se: C, 26.40; H,
1.77. Found: C, 25.59; H, 1.65%.
3.2. General procedure for the preparation of
CpW(CO)3SeSO2R (2)
The same procedure as given above for the preparation
of 1 was followed using sulfonyl chlorides instead of acid
chlorides. The products CpW(CO)3SeSO2R were eluted
with THF and recrystallized from CH2Cl2/hexane.
3.2.1. CpW(CO)3SeSO2C6H5 (2a)
Brown crystals (0.19 g, 12%). m.p. = 205–207 ꢁC (dec.).
IR (CHCl3, cmꢀ1): mC”O 2025 (s), 1935 (s); mSO 1263 (m),
2
1
1144 (m). H NMR (CDCl3): d 6.13 (s, 5H, C5H5); 7.55
(m, 3H, C6H5); 7.85 (m, 2H, C6H5). Anal. Calc. for
C14H10WO5SSe: C, 30.40; H, 1.82; S, 5.80. Found: C,
30.71; H, 1.52; S, 5.69%.
3.2.2. CpW(CO)3SeSO2-4-C6H4CH3 (2b)
Brown crystals (0.22 g,14%). m.p. = 135–137 ꢁC (dec.).
3.1.1. CpW(CO)3SeCOC6H5 (1a)
Orange crystals (0.21 g, 14%). m.p. = 111–113 ꢁC. IR
IR (CHCl3, cmꢀ1): mC”O 2037 (s), 2023 (s), 1938 (s); mSO
2
(CHCl3, cmꢀ1): mC”O 2032 (s), 1956 (s), 1935 (s); mC@O
1263 (m), 1144 (m). 1H NMR (CDCl3): d 2.45 (s, 3H,
CH3); 6.13 (s, 5H, C5H5); 7.31 (d, 2H, C6H4); 7.75 (d,
2H, C6H4). Anal. Calc. for C15H11WO5SSe: C, 31.77; H,
2.13; S, 5.65. Found: C, 31.45; H, 2.22; S, 5.55%.
1
1635 (w). H NMR (CDCl3): d 5.74 (s, 5H, C5H5); 7.51
(m, 3H, C6H5); 8.15 (m, 2H, C6H5). Anal. Calc. for
C15H10WO4Se: C, 34.85; H, 1.95. Found: C, 34.61; H,
2.03%.
3.2.3. CpW(CO)3SeSO2-4-C6H4OCH3 (2c)
Brown crystals (0.26 g, 16%). m.p. = 89–91 ꢁC (dec.). IR
3.1.2. CpW(CO)3SeCO-3,5-C6H3(NO2)2 (1b)
Brown-orange crystals (0.31 g, 18%). m.p. = 167–
169 ꢁC. IR (CHCl3, cmꢀ1): mC”O 2038 (s), 1962 (s), 1942
(CHCl3, cmꢀ1): mC”O 2037 (s), 2023 (s), 1939 (s); mSO 1264
2
(m), 1138 (m). 1H NMR (CDCl3): d 3.95 (s, 3H, CH3); 6.25

M. El-khateeb et al. / Inorganica Chimica Acta 359 (2006) 4259–4264
4263
(s, 5H, C5H5); 7.05 (d, 2H, C6H4); 7.84 (d, 2H, C6H4). Anal.
4. Supplementary materials
Calc. for C15H11WO6SSe: C, 30.89; H, 2.07; S, 5.50.
Found: C, 31.11; H, 2.19; S, 5.59%.
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre, (deposition
No. CCDC No. 277851) for compound 1c. Copies of this
information can be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ,
UK (fax: +44 1233 336 033; e-mail: deposit@ccdc.cam.
ac.uk or www: http://www.ccdc.cam.ac.uk).
3.2.4. CpW(CO)3SeSO2-4-C6H4Cl (2d)
Brown crystals (0.28 g, 17%). m.p. = 113–115 ꢁC (dec.).
IR (CHCl3, cmꢀ1): mC”O 2024 (s), 1935 (s); mSO 1261 (m),
2
1
1148 (m). H NMR (CDCl3): d 6.14 (s, 5H, C5H5); 7.49
(d, 2H, C6H4); 7.78 (d, 2H, C6H4). Anal. Calc. for
C14H9ClWO5SSe: C, 28.62; H, 1.54; S, 5.46. Found: C,
28.69; H, 1.51; S, 5.51%.
Acknowledgements
3.2.5. CpW(CO)3SeSO2CH3 (2e)
Brown powder (0.20 g, 14%). m.p. = 171–173 ꢁC (dec.).
We thank the Deanship of Research, Jordan University
of Science and Technology for financial support, grant no.
46/2004. We wish also to thank Prof. Stanislaw Ostrowski
(Institute of Chemistry, University of Podlasie, Poland) for
IR (CHCl3, cmꢀ1): mC”O 2042 (s), 2020 (s), 1937 (s); mSO
2
1263 (m), 1134 (m). 1H NMR (CDCl3): d 2.75 (s, 3H,
CH3); 6.15 (s, 5H, C5H5). Anal. Calc. for C9H8WO5SSe:
C, 22.02; H, 1.64; S, 6.53. Found: C, 22.64; H, 1.44; S,
6.60%.
1
measuring some H NMR spectra.
References
3.3. Crystallographic analysis of CpW(CO)3SeCO-3-
C6H4NO2 (1c)
[1] S. Narayan, V.K. Jain, K. Panneerselvam, T.H. Lu, S.F. Tung,
Polyhedron 18 (1999) 1253.
[2] S. Day, V.K. Jain, S. Chaudhury, A. Knoedler, F. Lissner, W. Kaim,
J. Chem. Soc. Dalton Trans. (2001) 723.
Single crystal suitable for X-ray were obtained by
recrystallization of 1c from CH2Cl2/hexane mixture. The
crystallographic data are shown in Table 2. The measure-
ments were at 293(2) K on a KappaCCD diffractometer.
There were 4584 independent reflections with 3771
observed reflections (>2r(I)). The structure was solved
by direct method using SHELXS97 (Sheldrick, 1997) and
difmap synthesis using SHELXTL96 (Sheldrick, 1996)
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Table 2
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Selected crystal data and refinement parameters for CpW(CO)3SeCO–3–
C6H4NO2 (1c)
Empirical formula
Crystal size (mm)
Crystal system
Space group
Volume (A )
Z
Unit cell dimensions
C15H9WO6NSe
0.10 · 0.09 · 0.08
monoclinic
P21/N
1569.4(3)
4
3
˚
˚
a (A)
7.0290(10)
21.857(2)
10.5420(10)
c = 90
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
104.30(5)
ꢀ9 < h < 9
0 < k < 30
0 < l < 14
562.04
Mo Ka
2.379
9.711
0.71070
Index range
Formula weight
Radiation type
Density (Mg mꢀ3
)
l (mmꢀ1
)
˚
k (A)
h (ꢁ)
1.860–30.04
0.0012(3)
0.1333
R[F2 > 2r(F2)]
xR(F2)a
2
a
x ¼ 1=½r2ðF o2Þ þ ð0:0598PÞ ꢁ, where P ¼ ðF o2 þ 2F 2c Þ=3.

4264
M. El-khateeb et al. / Inorganica Chimica Acta 359 (2006) 4259–4264
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