Preparation and organic transformation reactions of CpFe(CO)2SCO-3-C6H4-SO2Cl

Article abstract of DOI:10.1016/S0022-328X(02)02015-6

Treatment of the iron sulfides (μ-S_s)[CpFe(CO)₂]₂ with 3-ClCOC₆H₄SO₂Cl gave the novel organoiron thiocarboxylate complex CpFe(CO)₂SCO3-C₆H₄SO₂Cl which contains a free sulfonyl chloride group. This complex reacts with nucleophiles such as R₂NH, ArOH and RSH to give stable complexes CpFe b = 9.2395(2), c = 13.4341(4) A?, βB = 95.403(2)°, V = 2219.26(10) A?³ and Z = 4.

Full text of DOI:10.1016/S0022-328X(02)02015-6

Journal of Organometallic Chemistry 664 (2002) 228ꢂ233
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www.elsevier.com/locate/jorganchem
Preparation and organic transformation reactions of
CpFe(CO)2SCOÃ3-C6H4ÃSO2Cl
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Mohammad El-khateeb ꢀ, Aseel Younes
Chemistry Department, Faculty of Science, Jordan University of Science and Technology, P.O. Box 3030, Irbid 22110, Jordan
Received 22 July 2002; accepted 3 October 2002
Abstract
Treatment of the iron sulfides (m-Sx)[CpFe(CO)2]2 with 3-ClCOC6H4SO2Cl gave the novel organoiron thiocarboxylate complex
CpFe(CO)2SCOÃ3-C6H4SO2Cl which contains a free sulfonyl chloride group. This complex reacts with nucleophiles such as R2NH,
ArOH and RSH to give stable complexes CpFe(CO)2SCOÃ3-C6H4SO2NR2, CpFe(CO)2SCOÃ3-C6H4SO2OAr, and
CpFe(CO)2SCOÃ3-C6H4SO2SR, respectively. The crystal structure of CpFe(CO)2SCOÃ3-C6H4SO2N(CH3)CH2Ph has been
determined: space group: P21/c, aꢁ
# 2002 Elsevier Science B.V. All rights reserved.
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3
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17.9594(5), bꢁ
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9.2395(2), cꢁ
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13.4341(4) A, bꢁ
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95.403(2)8, Vꢁ
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2219.26(10) A and Zꢁ4.
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Keywords: Iron; Thiocarboxylate; Nucleophilic substitution; Structures; Sulfonates
1. Introduction
antibacterial effects. Both sulfur and selenium deriva-
tives showed mutagenic activity [12].
The reaction of the terephthaloyl chloride complexes
It has been demonstrated that organoiron sulfides and
CpFe(CO)2ECOÃ
/
4-C6H4COCl with organoiron sulfides
selenides, (m-Ex)[CpFe(CO)2]2 (Eꢁ
with acid chlorides to give the corresponding thio- or
seleno-carboxylate complexes, CpFe(CO)2ECOR [1ꢂ5].
Recently, the reactions of these sulfides or selenides with
sulfonyl chlorides were reported to give thio- or seleno-
sulfonate complexes, CpFe(CO)2ESO2R [6,7].
/
S, Se, xꢁ
/
1ꢂ
/
5) react
or selenides affords a large varity of homo bimetalic
bischalcogeno terephthalate complexes of the formula
/
CpFe(CO)2ECOC6H4COE?Fe(CO)2Cp? (Cp?ꢁ
ButC5H4, 1; 3-Bu2t C5H3) [8].
The important biological activity of sulfonyl-contain-
ing compounds [13ꢂ15] and our interest in organoiron
sulfur complexes prompted us to prepare the iron
3-C6H4SO2-
/
C5H5,
/
The organoiron thio- and seleno-terephthaloyl chlo-
ride complexes, CpFe(CO)2SCOÃ
/
4-C6H4COCl have
thiocarboxylate complex, CpFe(CO)2SCOÃ
/
been prepared by the reaction of the corresponding
sulfides or selenides complexes with terephthaloyl chlo-
ride [8]. These complexes have a reactive acyl chloride
Cl. The reactions of this complex with amines, phenols
and thiols are discussed in this paper.
group, which is reactive toward nucleophiles [9ꢂ11].
/
Nucleophiles such as amines, phenols, thiols and
organic acids were reported to react with these ter-
ephthaloyl chloride complexes and affords bifunctional
2. Results and discussion
The organoiron sulfides (m-Sx)[CpFe(CO)2]2 react
readily with 3-(chlorosulfonyl)benzoyl chloride in
diethyl ether at room temperature to give CpFe(CO)2-
complexes of the general formula CpFe(CO)2ECOÃ
/
4-
C6H4COY (YꢁNR2, OAr, SR, OCOR). Biological
/
studies on these complexes showed that these systems
have biological significance; selenium-containing com-
plexes were found to have antifungal activity and
SCOÃ/3-C6H4SO2Cl (1), as
a
stable solid and
CpFe(CO)2Cl which were separated by column chro-
matography (Scheme 1). The biiron complex
CpFe(CO)2SCOÃ
/
3-C6H4SO2SFe(CO)2Cp, which may
result from the reaction of the sulfonyl group with the
iron sulfides, could not be obtained from this reaction
ꢀ Corresponding author
E-mail address: kateeb@just.edu.jo (M. El-khateeb).
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 0 1 5 - 6

M. El-khateeb, A. Younes / Journal of Organometallic Chemistry 664 (2002) 228ꢂ
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229
Scheme 1. Yꢁ
/
NRR?:R, R?ꢁ
/
H, CH2Ph; H, 4-C6H4Cl; H, 4-C6H4NO2; CH3, CH2Ph; C2H5, C2H5; Ph, CH2Ph; Ph, Ph (2), OAr: Arꢁ
/
4-C6H4NO2,
4-C6H4Cl, 2,4-C6H3Cl2 (3), SR: Rꢁ
/
C2H5, Ph, C(CH3)3 (4).
even when excess of the iron sulfide was added. This
result is in agreement with our earlier finding that only
strongly electrophilic sulfonyl chlorides react with the
iron sulfides [6].
exhibited Cp-protons in the range 5.06ꢂ5.14 ppm,
/
suggesting similar environment around the Fe-centre.
These Cp-resonances agree well with the reported data
for CpFe(CO)2SCOR complexes [1,2]. The aromatic
protons and the protons for the sulfonyl-substituents are
shown in the spectra with the expected multiplicity and
chemical shift regions [6,14].
The IR spectrum of 1 shows two strong terminal
carbonyl bands at 2046, 2001 cmꢃ1, a medium band at
1605 cmꢃ1 for the thiocarboxylate group and two bands
at 1253, 1156 cmꢃ1 for the sulfonyl group. These bands
are similar to those obtained for comparable systems
The sulfonamide protons of complexes 2aꢂ
clearly observed in the IR and 1H-NMR spectra of these
complexes. The IR spectra of 2aꢂc show the NÃH band
in the range 3150ꢂ
3097 cmꢃ1 as a weak band, similar to
those observed for organic sulfonamides (3200ꢂ3050
cmꢃ1) [17ꢂ
22]. The reactivity of primary amines with 1
is greater than that of secondary amines.
The IR spectra of 2ꢂ4 exhibited two absorbances in
the regions 2046ꢂ2043 and 2001ꢂ
1997 (vs) cmꢃ1
/
c were
1
[1,6,16]. The H-NMR spectrum of 1 shows a singlet
/
/
peak at 5.07 ppm for the Cp-protons. The aromatic
protons appear as four peaks with the expected splitting
and chemical shifts.
Complex 1 has a sulfonyl chloride group which is
reactive with nucleophiles. The reactions of 1 with
primary amines, secondary amines, phenols and thiols
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/
/
/
/
/
consistant with the two terminal carbonyl groups
bonded to the iron centre. These absorbances are similar
gave CpFe(CO)2SCOÃ
CH2Ph; H, 4-C6H4Cl; H, 4-C6H4NO2, CH3, CH2Ph;
C2H5, C2H5; Ph, CH2Ph; Ph, Ph) (2), CpFe(CO)2SCOÃ
3-C6H4SO2OAr (Arꢁ4-C6H4NO2, 4-C6H4Cl, 2,4-
3-C6H4SO2SR (Rꢁ
/
3-C6H4SO2NRR? (R, R?ꢁH,
/
to those reported for CpFe(CO)2SCOÃ
(YꢁNR2, OAr, SR, OCOR) systems (2045ꢂ
2000ꢂ
1998 cmꢃ1) [8,9]. The spectra contain also a
medium band in the range 1606ꢂ
1599 cmꢃ1 for the
CÃO of the thiocarboxylate group. The sulfonyl group
reveals its presence through a strong absorptions at
1261ꢂ1249 and 1172ꢂ
1146 cmꢃ1 for the symmetric and
asymmeric SÃO stretching bands. These peaks are
within the range for the sulfonyl groups observed for
/
4-C6H4COY
/
/
/2051,
/
/
C6H3Cl2) (3), CpFe(CO)2SCOÃ
/
/
/
C2H5, Ph, C(CH3)3 (4), respectively, as shown in Scheme
1.
/
Complexes 2ꢂ4 were characterized by elemental
/
analysis, IR and 1H-NMR spectroscopy, and the results
are in agreement with the suggested structures. In
/
/
/
1
particular, the H-NMR spectra of all these complexes

230
M. El-khateeb, A. Younes / Journal of Organometallic Chemistry 664 (2002) 228ꢂ233
/
˚
Fig. 1. ORTEP drawing of CpFe(CO)2SCOÃ
2.100(4), FeÃC3ꢁ2.114(4), FeÃC4ꢁ2.086(4), FeÃ
C11ÃO11ꢁ1.224 (6), S2ÃO22ꢁ1.417(3), S2ÃO21ꢁ
93.94(16), C11ÃS1ÃFeꢁ107.16(11), O22ÃS2ÃO21ꢁ119.28(19), O22Ã
/
3-C6H4SO2N(CH3)CH2Ph (2d). Selected bond length (A) and angles (8): FeÃ
C5ꢁ2.065(4), FeÃC6ꢁ1.780(4), FeÃC7ꢁ1.774(4), FeÃS1ꢁ2.2714(9), SÃ
1.426(3), S2ÃN21ꢁ1.617(3), C7ÃFeÃS1ꢁ90.36(11), C6ÃFeÃS1ꢁ93.75(12), C6Ã
S2ÃN21ꢁ108.73(19), O21ÃS2ÃN21ꢁ107.16(17).
/
C1ꢁ
/
2.060(4), FeÃ
C11ꢁ1.740(3),
FeÃC7ꢁ
/
C2ꢁ
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CpFe(CO)2SSO2R and CpRu(PP)SSO2R (PPꢁ
dppm, dppe) [6,16] and for those observed for organic
sulfonamides [17ꢂ21].
/
2PPh3,
Nuclear magnetic resonance (NMR) spectra were
recorded on a Bruker-300 spectrophotometer. Samples
were prepared under nitrogen. Chemical shifts are in
ppm relative to Me4Si at 0 ppm. Infrared (IR) spectra
were recorded on a Nicolate 410-Impact Fourier-Trans-
form spectrophotometer. Elemental analyses were per-
/
The crystal structure of CpFe(CO)2SCOÃ
/
3-
C6H4SO2N(CH3)CH2Ph (2d), was determined and is
shown in Fig. 1. The cyclopentadienyl ring is bonded to
the Fe atom in an h5-fashion with FeÃ
/
C bond distances
formed by Laboratoire d’Analyse Ele´mentaire,
´
˚
ranging between 2.060(4) and 2.114(4) A which are
similar to those of CpFe(CO)2SCOÃ2-C6H4NO2 [1] and
CpFe(CO)2SSO2CCl3 [7]. The compound has an FeÃ
University of Montre´al, Montre´al, Que´bec, Canada.
Melting points were measured on an Electrothermal
melting point apparatus and are uncorrected.
/
/S
˚
bond length of 2.2714(9) A, is also similar to those of
CpFe(CO)2SCOÃ2-C6H4NO2, [1] and CpFe(CO)2S-
SO2CCl3 [7]. The CÃO bond length (of thiocarboxylate)
is 1.224(4) A is longer than the corresponding CÃO of
2-C6H4NO2 [1] (1.209(5) A). This
/
3.1. Preparation of CpFe(CO)2SCOÃ
/
3-C6H4SO2Cl (1)
/
˚
/
A solution of the acid chloride 3-ClCOC6H4SO2Cl
(0.86 g, 3.61 mmol) in Et2O (10 ml) was added at room
˚
CpFe(CO)2SCOÃ
/
might be due to the important withdrawing effect of
the ortho nitro group related to meta sulfonyl group.
temperature (r.t.) to a reddishꢂ/brown solution (2.82
mmol) of (m-Sx)[CpFe(CO)2]2 (xꢁ/3 or 4) in Et2O (60
The SÃ
sulfonamides [19]. The S2 atom shows a distorted
tetrahedral arrangement. The largest angle is the O22Ã
S2ÃO21 angle (119.28(19)8) and the smallest is O21Ã
S2ÃC14 (106.15(17)8).
/
O bonds are similar to those of organic
ml). The resulting mixture was stirred overnight at r.t.
The volatiles were removed under vacuum and the
residue was redissolved in a minimum amount of
methylene chloride and introduced to a silica gel column
made up in C6H14. Elution with a mixture of CH2Cl2
/
/
/
/
and C6H14 (1:1 volume ratio) gave a brownishꢂ
band which was collected and identified as
CpFe(CO)2SCOÃ3-C6H4SO2Cl, followed by red
band which was identified as CpFe(CO)2Cl. The title
complex was re-crystallized from CH2Cl2ꢂC6H14.
/
orange
/
a
3. Experimental
/
All experiments were performed under N2 atmosphere
using Schlenk techniques [23]. Benzene, Et2O, THF and
C6H14 were distilled over sodium/benzophenone under
N2 prior to use. Methylene chloride was distilled over
P2O5. The reagents, [CpFe(CO)2]2, suflur 3-(chlorosul-
fonyl)benzoyl chloride, amines, alcohols and thiols
(Acros or Aldrich) were used as received. Iron sulfides
(m-Sx)[CpFe(CO)2]2 were prepared as described in the
literature [24].
3.1.1. CpFe(CO)2SCOÃ
/
3-C6H4SO2Cl (1)
105ꢂ ,
107 8C. IR (cmꢃ1
Yield: 1.29 g (78%). M.p.ꢁ
/
/
CH2Cl2) 2046, 2001 (nCO), 1605 (nCÄO), 1253, 1156 (nSO).
1H-NMR (CDCl3): d 5.07 (s, 5H, Cp), 7.60 (bt, 1HC,
ArÃ
/
H), 8.06 (m, 1HD, ArÃ
/
H), 8.41 (m, 1HB, ArÃ
/
H),
H). Anal. Calc. for C14H9ClFeO5S2:
8.78 (s, 1HA, ArÃ
/
C, 40.73; H, 2.20; S, 15.51. Found: C, 41.08; H, 2.00; S,
15.61%.

M. El-khateeb, A. Younes / Journal of Organometallic Chemistry 664 (2002) 228ꢂ
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231
1
3.2. General procedure for the preparation of
CpFe(CO)2SCOÃ3-C6H4SO2Y
(nCÄO), 1251, 1146 (nSO). H-NMR (CDCl3): d 1.23 (t,
6H, CH2CH3), 3.22 (q, 4H, CH2CH3); 5.09 (s, 5H, Cp),
/
7.95 (bt, 1HC, ArÃ
/
H), 8.22ꢂ
/
8.49 (m, 2H, ArÃ/H), 8.56
A THF solution (70 ml) containing YH (1.45 mmol)
and CpFe(CO)2SCOÃ3-C6H4SO2Cl (0.30 g, 0.72 mmol)
(s, 1HA, ArÃH). Anal. Calc. for C18H19FeO5S2N: C,
50.79; H, 3.14; N, 3.12. Found: C, 50.85; H, 3.07; N,
2.98%.
/
/
was refluxed. The volatiles were removed under vacuum
and the residue was redissolved in CH2Cl2 and trans-
ferred to a chromatographic column made up in C6H14.
3.2.6. CpFe(CO)2SCOÃ
Yield: 0.30 g (75%). M.p.ꢁ
timeꢁ
7 h. IR (cmꢃ1, CH2Cl2) 2044, 1999 (nCO), 1604
(nCÄO), 1252, 1155 (nSO). H-NMR (CDCl3): d 4.75 (s,
2H, CH2), 5.08 (s, 5H, Cp), 7.21ꢂ7.54 (m, 10H, 2Ph),
7.67ꢂ8.48 (m, 4H, ArÃH). Anal. Calc. for
/
3-C6H4SO2N(Ph)CH2Ph (2f)
An orange band was eluted with Et2Oꢂ
band was collected and identified as CpFe(CO)2SCOÃ
C6H4SO2Y, and re-crystallized from CH2Cl2ꢂC6H14.
/C6H14. This
/
126ꢂ129 8C. Reflux
/
/
3-
/
1
/
/
3.2.1. CpFe(CO)2SCOÃ
Yield: 0.26 g (76%). M.p.ꢁ
timeꢁ
4 h. IR (cmꢃ1, CH2Cl2) 2044, 1999 (nCO), 1605
/
3-C6H4SO2NHCH2Ph (2a)
/
/
/
117ꢂ118 8C. Reflux
/
C27H21FeO5S2N: C, 57.97; H, 3.78; N, 2.50. Found: C,
/
57.80; H, 3.76; N, 2.45%.
1
(nCÄO), 1252, 1153 (nSO). H-NMR (CDCl3): d 4.15 (m,
2H, CH2), 4.75 (t, 1H, NH), 5.09 (s, 5H, Cp), 7.35 (m,
3.2.7. CpFe(CO)2SCOÃ
/
3-C6H4SO2NPh2 (2g)
5H, Ph), 7.52 (bt, 1HC, ArÃ
/
H), 8.10ꢂ
/
8.57 (m, 2H, ArÃ
/
Yield: 0.23 g (58%). M.p.ꢁ
/
95ꢂ
/
97 8C. Reflux timeꢁ
/
H), 8.65 (s, 1HA, ArÃ
/
H). Anal. Calc. for
6 h. IR (cmꢃ1, CH2Cl2) 2045, 1999 (nCO), 1604 (nCÄO),
1253, 1159 (nSO). 1H-NMR (CDCl3): d 5.14 (s, 5H, Cp),
C21H17FeO5S2N: C, 52.18; H, 3.54; N, 2.95. Found: C,
52.52; H, 3.62; N, 3.22%.
7.32ꢂ
/
7.67 (m, 10H, 2Ph), 7.81ꢂ H).
Anal. Calc. for C26H19FeO5S2N: C, 57.26; H, 3.51; N,
/
8.65 (m, 4H, ArÃ
/
3.2.2. CpFe(CO)2SCOÃ
(2b)
Yield: 0.23 g (64%). M.p.ꢁ
timeꢁ
5 h. IR (cmꢃ1, CH2Cl2) 2045, 2001 (nCO), 1604
(nCÄO), 1253, 1156 (nSO). H-NMR (CDCl3): d 4.82 (s,
1H, NH), 5.07 (s, 5H, Cp), 7.25ꢂ7.89 (m, 4H, ArÃH),
8.12ꢂ8.79 (m, 4H, ArÃH). Anal. Calc. for
/
3-C6H4SO2NHÃ
/
4-C6H4Cl
2.57. Found: C, 57.51; H, 2.96; N, 2.25%.
/
122ꢂ
/
123 8C. Reflux
3.2.8. CpFe(CO)2SCOÃ
/
3-C6H4SO2OÃ/4-C6H4NO2
/
(3a)
1
Yield: 0.19 g (51%). Reflux timeꢁ
/
12 h. M.p.ꢁ
/
99ꢂ
/
/
/
102 8C. IR (cmꢃ1, CH2Cl2) 2046, 2001 (nCO), 1599
1
/
/
(nCÄO), 1261, 1164 (nSO). H-NMR (CDCl3): d 5.12 (s,
C20H14ClFeO5S2N: C, 47.59; H, 2.79; N, 2.77. Found:
5H, Cp), 7.26ꢂ
ArÃH). Anal. Calc. for C20H13FeO8S2N: C, 46.62; H,
2.54; N, 2.72. Found: C, 47.55; H, 3.31; N, 2.62%.
/
7.73 (m, 4H, ArÃ
/
H), 7.80ꢂ
/
8.87 (m, 4H,
C, 47.59; H, 2.78; N, 2.72%.
/
3.2.3. CpFe(CO)2SCOÃ
(2c)
Yield: 0.29 g (78%). M.p.ꢁ
timeꢁ
4.5 h. IR (cmꢃ1, CH2Cl2) 2045, 2000 (nCO),
1601 (nCÄO), 1253, 1157 (nSO). 1H-NMR (CDCl3): d 2.68
(br, 1H, NH), 5.08 (s, 5H, Cp), 7.26ꢂ7.85 (m, 4H, ArÃ
H), 8.13ꢂ8.73 (m, 4H, ArÃH). Anal. Calc. for
/
3-C6H4SO2NHÃ
/
4-C6H4NO2
3.2.9. CpFe(CO)2SCOÃ
/
3-C6H4SO2OÃ
/
4-C6H4Cl (3b)
/
115ꢂ
/
116 8C. Reflux
Yield: 0.18 g (49%). Reflux timeꢁ
/
12 h. M.p.ꢁ
/
94ꢂ
/
/
96 8C. IR (cmꢃ1, CH2Cl2) 2045, 2000 (nCO), 1604
(nCÄO), 1246, 1157 (nSO). H-NMR (CDCl3): d 5.10 (s,
1
/
/
5H, Cp), 7.26ꢂ
ArÃH). Anal. Calc. for C20H13FeO6S2Cl: C, 47.59; H,
2.59. Found: C, 47.50; H, 3.02%.
/
7.51 (m, 4H, ArÃ
/
H), 7.75ꢂ
/
8.90 (m, 4H,
/
/
/
C20H14FeO7S2N2: C, 46.71; H, 2.74; N, 5.45. Found:
C, 46.65; H, 3.06; N, 5.15%.
3.2.10. CpFe(CO)2SCOÃ
/
3-C6H4SO2OÃ
/
2,4-C6H3Cl2
3.2.4. CpFe(CO)2SCOÃ
(2d)
Yield: 0.28 g (78%). M.p.ꢁ
timeꢁ
6 h. IR (cmꢃ1, CH2Cl2) 2044, 1999 (nCO), 1605
(nCÄO), 1249, 1155 (nSO). H-NMR (CDCl3): d 2.55 (s,
3H, Me), 4.24 (m, 2H, CH2Ph), 5.09 (s, 5H, Cp), 7.37
/
3-C6H4SO2N(CH3)CH2Ph
(3c)
Yield: 0.19 g (50%). Reflux timeꢁ
/
12 h. M.p.ꢁ
/
101ꢂ
/
/
121ꢂ
/
124 8C. Reflux
103 8C. IR (cmꢃ1, CH2Cl2) 2046, 2001 (nCO), 1605
1
/
(nCÄO), 1245, 1162 (nSO). H-NMR (CDCl3): d 5.11 (s,
1
5H, Cp), 7.26ꢂ
ArÃH). Anal. Calc. for C20H12Cl2FeO6S2: C, 44.55; H,
2.24. Found: C, 44.73; H, 2.17%.
/
7.75 (m, 3H, ArÃ
/
H), 7.84ꢂ
/
8.89 (m, 4H,
/
(m, 5H, Ph), 7.53 (bt, 1HC, ArÃ
/
H), 8.28ꢂ
/
8.51 (m, 2H,
ArÃH); 8.75 (s, 1HA, ArÃH). Anal. Calc. for
/
/
C22H15FeO5S2N: C, 53.13; H, 3.85; N, 2.85. Found: C,
52.31; H, 3.79; N, 2.66%.
3.2.11. CpFe(CO)2SCOÃ
/
3-C6H4SO2SC2H5 (4a)
Yield: 0.19 g (62%). Reflux timeꢁ
/
8 h. M.p.ꢁ
/
111ꢂ
/
114 8C. IR (cmꢃ1, CH2Cl2) 2045, 2000 (nCO), 1606
1
3.2.5. CpFe(CO)2SCOÃ
Yield: 0.27 g (85%). M.p.ꢁ
timeꢁ
7 h. IR (cmꢃ1, CH2Cl2) 2043, 1997 (nCO), 1605
/
3-C6H4SO2N(C2H5)2 (2e)
(nCÄO), 1254, 1172 (nSO). H-NMR (CDCl3): d 1.32 (t,
3H, CH2CH3), 4.20 (q, 2H, CH2CH3), 5.09 (s, 5H, Cp),
/
128ꢂ130 8C. Reflux
/
/
7.89ꢂ
/
8.79 (m, 4H, ArÃ
/H). Anal. Calc. for

232
M. El-khateeb, A. Younes / Journal of Organometallic Chemistry 664 (2002) 228ꢂ233
/
C16H14FeO6S3: C, 43.84; H, 3.22. Found: C, 43.40; H,
3.11%.
4. Supplementary material
Further details of the structure determination may be
obtained from Cambridge Crystallographic Data Cen-
tre, CCDC no. 187632. Copies of this information may
be obtained free of charge from The Director, CCDC,
3.2.12. CpFe(CO)2SCOÃ
/
3-C6H4SO2SPh (4b)
Yield: 0.16 g (45%). Reflux timeꢁ
/
9 h. M.p.ꢁ
/
122ꢂ
/
124 8C. IR (cmꢃ1, CH2Cl2) 2044, 1999 (nCO), 1601
1
12 Union Road, Cambridge CB2 1EZ, UK (Fax: ꢄ44-
/
(nCÄO), 1251, 1160 (nSO). H-NMR (CDCl3): d 5.06 (s,
1233-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
5H, Cp), 7.25ꢂ
H). Anal. Calc. for C20H14FeO5S3: C, 49.39; H, 2.90.
Found: C, 49.45; H, 2.85%.
/
7.79 (m, 5H, Ph), 7.85ꢂ
/
8.92 (m, 4H, ArÃ
/
3.2.13. CpFe(CO)2SCOÃ
/
3-C6H4SO2SC(CH3)3 (4c)
Acknowledgements
Yield: 0.19 g (57%). Reflux timeꢁ
/
9 h. M.p.ꢁ
/
128ꢂ
/
131 8C. IR (cmꢃ1, CH2Cl2) 2045, 2002 (nCO), 1605
The authors thank the Deanship of Research, Jordan
University of Science & Technology for financial sup-
port, Grant No. 157/2001. Madam F. Be´langer-Garie´py
(University of Montre´al) is greatly thanked for deter-
mining the X-ray structure.
1
(nCÄO), 1251, 1160 (nSO). H-NMR (CDCl3): d 2.23 (m,
9H, tBu), 5.09 (s, 5H, Cp), 7.25 (bt, 1HC, ArÃ
/
H), 8.14ꢂ
/
8.57 (m, 2H, ArÃ
/
H), 8.81 (s, 1HA, ArÃ
/H). Anal. Calc.
for C18H18FeO5S3: C, 46.36; H, 2.90. Found: C, 46.27;
H, 2.97%.
3.3. Crystallographic analysis of CpFe(CO)2SCOÃ
/
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P21/c
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˚
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17.9594(5)
9.2395(2)
˚
b (A)
˚
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13.4341(4)
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˚
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/
R[F2ꢀ2s(F2)]
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a
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¨ ¨
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¨
¨