Substitution reactions of mono-, di- and tri-thiocarbonato complexes of iron

Article abstract of DOI:10.1016/j.poly.2017.05.016

The photolytic reactions of iron thiocarbonato complexes CpFe(CO)₂SC(Y)Y′R [Y?=?Y′?=?O; R?=?2-C₆H₄Cl (1), 4-C₆H₄Cl (2); Y?=?S, Y′?=?O; R?=?C₆H₄F (3), Y?=?Y′?=?S; R?=?Ph (4)] with EPh₃ (E?=?P, As, Sb) are performed. Monosubstituted complexes of the general formula CpFe(CO)(EPh₃)SC(Y)Y′R [Y?=?Y′?=?O; R?=?2-C₆H₄Cl (5), 4-C₆H₄Cl (6); Y?=?S, Y′?=?O; R?=?C₆H₄F (7), Y?=?Y′?=?S; R?=?Ph (8); E?=?P (a), As (b), Sb (c)] have been isolated and characterized by spectroscopic analysis (UV–Vis, IR, ¹H, ³¹P NMR) and elemental analysis. The molecular structures of CpFe(CO)(PPh₃)SCO₂-2-C₆H₄Cl (5a) and its dicarbonyl parent CpFe(CO)₂SCO₂-2-C₆H₄Cl (1) have been determined by single crystal X-ray crystallographic studies.

Full text of DOI:10.1016/j.poly.2017.05.016

Accepted Manuscript
Substitution Reactions of Mono-, Di- and Tri-thiocarbonato Complexes of Iron
Mohammad El-khateeb, Alaa Mansor, Ibrahim Jibril, Tobias Rüffer, Heinrich
Lang
PII:
S0277-5387(17)30352-2
DOI:
http://dx.doi.org/10.1016/j.poly.2017.05.016
POLY 12635
Reference:
Polyhedron
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Accepted Date:
25 April 2017
9 May 2017
Please cite this article as: M. El-khateeb, A. Mansor, I. Jibril, T. Rüffer, H. Lang, Substitution Reactions of Mono-,
Di- and Tri-thiocarbonato Complexes of Iron, Polyhedron (2017), doi: http://dx.doi.org/10.1016/j.poly.2017.05.016
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Substitution Reactions of Mono-, Di- and Tri-thiocarbonato
Complexes of Iron
Mohammad El-khateeb*,a, Alaa Mansora, Ibrahim Jibrilb, Tobias Rüfferc, Heinrich Langc
a ChemistryDepartment, Jordan University of Science and Technology, Irbid, 22110
JORDAN
b Chemistry Department, Yarmouk University, Irbid, JORDAN
c Institut für Chemie, Fakultät für Naturwissenschaften, Technische Universität Chemnitz, D-
09107 Chemnitz, GERMANY
Abstract
The photolytic reactions of iron thiocarbonato complexes CpFe(CO)2SC(Y)Y'R [Y= Y'= O;
R= 2-C6H4Cl (1), 4-C6H4Cl (2); Y= S, Y'= O; R= C6H4F (3), Y= Y' = S; R= Ph (4)] with
EPh3 (E = P, As, Sb) are performed. Monosubstituted complexes of the general formula
CpFe(CO)(EPh3)SC(Y)Y'R [Y= Y'= O; R= 2-C6H4Cl (5), 4-C6H4Cl (6); Y= S, Y'= O; R=
C6H4F (7), Y= Y' = S; R= Ph (8); E= P (a), As (b), Sb (c)] have been isolated and
1
characterized by spectroscopic analysis (UV-Vis, IR, H-, 31P-NMR) and elemental analysis.
The molecular structures of CpFe(CO)(PPh3)SCO2-2-C6H4Cl (5a) and its dicarbonyl parent
CpFe(CO)2SCO2-2-C6H4Cl (1) have been determined by single crystal X-ray crystallographic
studies.
Keywords: Iron, Thiocarbonate, Substitution, Sulfur, Complexes, Structures.
1. Introduction
Iron carbonyl complexes undergo smooth substitution of one or more CO groups
generating a number of different products [1-10]. Reactions of CpFe(CO)2X (X= SPh,
SiMe3, SnMe3, SnPh3) with PMe3 gave the mono-substituted CpFe(CO)(PMe3)X and the di-
substituted CpFe(PMe3)2X products [1]. The reaction of CpFe(CO)2Me with PMe3 gave
either the inserted product CpFe(CO)(PMe3)COMe or the di-substituted one CpFe(PMe3)2Me
depending on the reaction conditions [2]. On the other hand, the photolytic reaction of the
ethyl derivative CpFe(CO)2Et with L (= P(OMe)3, PMe3) gave the mono and the disubstituted

complexes in addition to the hydrides CpFe(CO)(L)H and CpFe(L)2H [3]. The silyl complex
CpFe(CO)2SiH3 reacted with various donors (L= PMe3, PPh3, MeNC, t-BuNC) to give
CpFe(CO)(L)SiH3 and CpFe(L)2SiH3 via stepwise CO substitution [4-6].
The CO-substitution reactions of iron thiocarboxylato complexes have been
investigated in our lab. The reaction of the these complexes (CpFe(CO)2SCOR) with ER3
ligands produced the mono-substituted complexes CpFe(CO)(ER3)SCOR' (E= P, R= Ph, OEt,
E= As, Sb, R= Ph, R'= alkyl, aryl, heterocycle) [11,12]. The reactions of these
thiocarboxylato complexes with Ph2P(CH2)nPPh2 (n= 1-6) gave either the mono-substituted
complexes CpFe(CO)(P-Ph2P(CH2)nPPh2)SCOR for n= 1-6 or the di-substituted complexes
CpFe(2P,P-Ph2P(CH2)nPPh2)SCOR only for n= 1 and 2 [13,14]. The ethyldithiocarbonato
complexes Cp'Fe(CO)2SCSOEt (Cp'= C5H5, C5Me5) reacted with phosphine or phosphite
ligands (= L) to form Cp'Fe(CO(L)SCSOEt [15,16].
Thiocarbonato metal complexes have found application in different fields [17-24]. In
the medical field, thiocarbonates are used against HIV infections, have antitumor
properties [17, 18] and are of great importance for treating Alzheimer’s disease [19].
Industrially, they have been used for nanoparticles of metal sulfides production
[20,21] and corrosion inhibitors [22]. In agriculture, metal thiocarbonates are used as
pesticides [23] and herbicide [24]. This importance prompted us to synthesize
thiocarbonate complexes of iron [25-27]. As a continuation to our efforts on the area of
thiocarbonate complexes of iron, herein, we report the CO-substitution reactions of iron
mono-, di- and tri-thiocarbonato complexes by EPh3 donors. The molecular structures of two
complexes are presented.
Experimental
Materials and Methods
Synthesis and manipulations were performed under an atmosphere of nitrogen using
standard Schlenk line techniques. The following solvents: tetrahydrofuran, diethyl ether,
hexane were dried over sodium/benzophenone and CH2Cl2 was dried over P2O5 following
standard procedure. The compounds triphenylphosphine, triphenylarsine, triphenylantimony
were used as received (Acros) while CpFe(CO)2SC(Y)Y'R are prepared following reported

procedures [25-27]. Silica gel of particle size 0.063-0.200 mm (70-230 mesh) was used for
column chromatography after drying at 110 ᵒC for several days.
Bruker-Avance 400 MHz spectrometer was used to measure the nuclear magnetic
resonance (NMR) spectra of the synthesized complexes. Chemical shifts are reported relative
to TMS at 0 ppm for 1H-NMR and relative to H3PO4 (as external standard) for 31P-NMR and
are reported in ppm. Melting points were reported on an electrothermal melting point
apparatus and are uncorrected. Elemental analyses were performed using a vairo EL III
CHNS (Elemental analyse GmbH Hanau) as single determination. The UV-Vis and IR
spectra were recorded on a Shimadzu 240-UV–Vis and a JASCO FT-IR spectrophotometer,
respectively. The photolytic reactions were carried out using a low pressure mercury lamp
(Herauios).
Synthesis of CpFe(CO)(EPh3)SC(S)O-2-C6H4Cl 1
The compound is prepared following the reported procedure [26]. Orange (88%). m.p.: 105-
106 ˚C. IR (CH2Cl2, cm-1): νC≡O 2042, 1994 (s); νSeC=O 1670 (m). 1H-NMR (CDCl3): 5.05 (s,
5H, C5H5), 6.80 (m, 2H, C6H4), 7.33 (m, 2H, C6H4). Anal. Calc. for C14H9ClFeO4S: C, 46.12;
H, 2.49; S, 8.80%. Found: C, 45.90; H, 2.48; S, 8.32%.
General Procedure for the Preparation of CpFe(CO)(EPh3)SC(Y)Y'R 5-8
A mixture of CpFe(CO)2SC(Y)Y'R (1.00 mmol) and EPh3 (1.10 mmol) was dissolved in 50
mL THF and the solution is irradiated by UV-light at 0 ˚C for 60 – 90 min until the
disappearance of the spot of the starting dicarbonyl complexes as indicated by TLC. The
volatiles were removed under reduced pressure and the resulting solid was re-dissolved in ca.
2 mL of CH2Cl2 and chromatographed. The column was eluted with hexane to remove any
unreacted EPh3 ligand and then with hexane/diethyl ether solution (1:1 V:V) which gave a
dark red band of the products. The products were recrystallized by layering hexane on
CH2Cl2 solution of them and kept overnight at -4 ˚C. In some experiments, another red band
was collected and identified as the chelate complexes CpFe(CO)(2S,S-SC(S)Y'R).
CpFe(CO)(PPh3)SCO2-2-C6H4Cl 5a Brown (61%). m.p.: 115-116 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1955 (s); νSC=O 1674 (m). H-NMR (CDCl3): 4.51 (s, 5H, C5H5), 7.03 (m, 2H, C6H4),

31
7.18 (m, 2H, C6H4), 7.37 (m, 15H, PPh3). P-NMR (CDCl3): δ 68.0. UV–Vis. in CH2Cl2:
λmax (nm) (εmax, M-1cm-1): 402 (3.2 × 104). Anal. Calc. for C31H24ClFeO3PS: C, 62.17; H,
4.04; S, 5.35%. Found: C, 62.17; H, 4.19; S, 4.84%.
CpFe(CO)(AsPh3)SCO2-2-C6H4Cl 5b Dark red (56%). m.p.: 131-132 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1951 (s); νSC=O 1675 (m). H-NMR (CDCl3): 4.63 (s, 5H, C5H5), 7.18 (m, 2H, C6H4),
7.34 (m, 2H, C6H4), 7.48 (m, 15H, AsPh3). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1):
395 (6.6 × 104). Anal. Calc. for C31H24ClFeO3AsS: C, 57.32; H, 3.76; S, 4.99%. Found: C,
57.60; H, 3.65; S, 4.54%.
CpFe(CO)(SbPh3)SCO2-2-C6H4Cl 5c Brown (44%). m.p.: 120-122 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1924 (s); νSC=O 1666 (m). H-NMR (CDCl3): 4.75 (s, 5H, C5H5), 6.63 (m, 2H, C6H4),
7.16 (m, 2H, C6H4), 7.41 (d, 15H, SbPh3). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1): 404
(3.5 × 104). Anal. Calc. for C31H24ClFeO3SbS: C, 53.99; H, 3.51; S, 4.65%. Found: C, 53.74;
H, 3.67; S, 4.33%.
CpFe(CO)(PPh3)SCO2-4-C6H4Cl 6a Brown (65%). m.p.: 110-111 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1988 (s); νSC=O 1674 (m). H-NMR (CDCl3): 4.57 (s, 5H, C5H5), 7.03 (d, 2H, C6H4),
7.29 (d, 2H, C6H4), 7.44 (m, 15H, PPh3). 31P-NMR (CDCl3): δ 71.2. UV–Vis. in CH2Cl2: λmax
(nm) (εmax, M-1cm-1): 398 (5.0 × 104). Anal. Calc. for C31H24ClFeO3PS: C, 62.17; H, 4.04; S,
5.35%. Found: C, 61.42; H, 3.78; S, 5.12%.
CpFe(CO)(AsPh3)SCO2-4-C6H4Cl 6b (51%). m.p.: 131-132 ˚C. IR (CH2Cl2, cm-1): νC≡O
1956 (s); νSC=O 1672 (m). 1H-NMR (CDCl3): 4.60 (s, 5H, C5H5); 6.93 (d, 2H, C6H4), 7.19 (d,
2H, C6H4), 7.37 (m, 15H, AsPh3). UV–Vis. in CH2Cl2: λmax(nm) (εmax, M-1cm-1): 405 (4.8 ×
104). Anal. Calc. for C31H24ClFeO3AsS: C, 57.32; H, 3.76; S, 4.99%. Found: C, 57.20; H,
3.65; S, 4.67%.
CpFe(CO)(SbPh3)SCO2-4-C6H4Cl 6c Brown (42%). m.p.: 130-132 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1947 (s); νSC=O 1647 (m). H-NMR (CDCl3): 4.67 (s, 5H, C5H5), 7.09 (d, 2H, C6H4),
7.34 (d, 2H, C6H4), 7.44 (m, 15H, SbPh3). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1): 401
(7.2 × 104). Anal. Calc. for C31H24ClFeO3SbS: C, 53.99; H, 3.51; S, 4.65%. Found: C, 53.65;
H, 3.70; S, 4.20%.
CpFe(CO)(PPh3)SC(S)O-4-C6H4F 7a (55%). Brown. m.p.: 125-126˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1942 (s); νSC=O 1581 (m). H-NMR (CDCl3): 4.59 (s, 5H, C5H5), 7.09 (d, 2H, C6H4),
7.44 (d, 2H, C6H4), 7.42 (m, 15H, PPh3). 31P-NMR (CDCl3): δ 73.0. UV–Vis. in CH2Cl2:

λmax (nm) (εmax, M-1cm-1): 370 (5.3 × 104). Anal. Calc. for C31H24FFeO2PS2: C, 62.21; H,
4.04; S, 10.72%. Found: C, 62.25; H, 4.24; S, 9.96%.
CpFe(CO)(AsPh3)SC(S)O-4-C6H4F 7b (68%). Red. m.p.: 135-136 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1990 (s); νSC=O 1504 (m). H-NMR (CDCl3): 4.60 (s, 5H, C5H5), 6.69 (d, 2H, C6H4),
7.03 (d, 2H, C6H4), 7.14 (m, 15H, AsPh3). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1):
378 (5.5 × 104). Anal. Calc. for C31H24FFeO2AsS2: C, 57.96; H, 3.77; S, 9.98%. Found: C,
58.63; H, 3.54; S, 9.93%.
CpFe(CO)(PPh3)SC(S)O-4-C6H4F 7c Brown. (64%). m.p.: 149-150 ˚C. IR (CH2Cl2, cm-1):
1
νC≡O 1942 (s); νSC=O 1449 (m). H-NMR (CDCl3): 4.66 (s, 5H, C5H5), 6.85 (d, 1H, C6H4),
7.09 (d, 1H, C6H4), 7.10 (m, 15H, SbPh3). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1): 386
(1.2 × 104). Anal. Calc. for C31H24FFeO2S2Sb: C, 54.02; H, 3.51; S, 9.30%. Found: C, 53.98;
H, 3.41; S, 8.44%.
CpFe(CO)(PPh3)SCS2C6H5 8a Brwon (48%). m.p.: 142-143 ˚C. IR (CH2Cl2, cm-1): νC≡O
1941 (s); νSC=O 1589 (m). 1H-NMR (CDCl3): 4.61 (s, 5H, C5H5), 7.11 (m, 3H, C6H5), 7.46 (d,
2H, C6H5), 7.48 (m, 15H, PPh3). 31P-NMR (CDCl3): δ 77.5. UV–Vis. in CH2Cl2: λmax (nm)
(εmax, M-1cm-1): 364 (3.3 × 104). Anal. Calc. for C31H26FeOPS3: C, 62.41; H, 4.22; S,
16.13%. Found: C, 63.22; H, 4.47; S, 16.23%.
CpFe(CO)(AsPh3)SCS2C6H5 8b Red (58%). m.p.: 158-160˚C. IR (CH2Cl2, cm-1): νC≡O 1932
1
(s); νSC=O 1573 (m). H-NMR (CDCl3): 4.49 (s, 5H, C5H5), 6.94 (m, 3H, C6H5), 7.38 (d, 1H,
C6H5), 7.39 (m, 15H, AsPh3). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1): 374 (4.6 × 104).
Anal. Calc. for C31H25FeOAsS3: C, 58.13; H, 3.39; S, 15.02%. Found: C, 58.54; H, 3.51; S,
15.20%.
CpFe(CO)(SbPh3)SCS2C6H5 8c Brown (62%). m.p.: 158-159 ˚C. IR (CH2Cl2, cm-1): νC≡O
1923 (s); νSC=O 1648 (m). 1H-NMR (CDCl3): 4.75 (s, 5H, C5H5), 6.95 (m, 3H, C6H5), 7.36 (m,
15H, SbPh3); 7.42 (d, 2H, C6H5). UV–Vis. in CH2Cl2: λmax (nm) (εmax, M-1cm-1): 365 (1.9 ×
104). Anal. Calc. for C31H25FeOS3Sb: C, 54.17; H, 3.67; S, 14.00%. Found: C, 54.37; H,
3.57; S, 13.64%.

Crystal Structure Determination
Crystallographic data, data collection and refinement parameters for 5a (120 K, Mo K
radiation) and 1 (120 K, Cu K radiation) are summarized in Table 1. The structures were
solved by direct methods (SHELXS-2013 [28]) and refined by full-matrix least squares
techniques against F2 (SHELXL-2013 [28]). All non-hydrogen atoms were refined
anisotropically and all hydrogen atoms were included at calculated positions with default
SHELXL-2013 constraints. In case of 1 the C6H4ClO group composed of the atoms C9C14,
Cl1 and O4 was refined disordered with split occupancies of 0.55/0.45.
Table 1: Crystallographic data and refinement details for CpFe(CO)2SCO2-2-C6H4Cl, 1 and
CpFe(CO)(PPh3)SCO2-2-C6H4Cl, 5a
5a
1
Empirical formula
C31H24ClFeO3PS
598.83
C14H9ClFeO4S
364.57
Formula weight
(g/mol)
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell dimension
a (Å)
120
0.71073
monoclinic
P21/n
120
1.54184
monoclinic
C2/c
9.7885(2)
13.5466(3)
20.6635(5)
90
96.571(2)
90
22.4764(5)
9.0964(2)
14.0733(3)
90
92.048(2)
90
b (Å)
c (Å)
 (°)
 (°)
 (°)
Volume (Å)
2722.00(11)
2875.51(11)
Z
4
8
Density(calculate)
Mg/m3
1.461
1.684
Absorption coefficient
0.820
11.599
mm–1
F(000)
1232
1472
Theta range for data
collection (°)
Indices ranges
3.007 to 24.999
5.246 to 66.453
–11  h  11
–16  k  15
–24  l  24
11922
–21  h  26
–9  k  10
–16  l  16
4294
Reflections collected
Independent
reflections
Completeness (%),
4764
2501
Rinta = 0.0294
99.3,
Rinta = 0.0233
98.5,

24.999
66.453

max (°)
Data / restraints /
parameters
4764 / 0 / 343
2501 / 4 / 239
Goodness-of-fit on
1.004
1.025
F2b
Final R indices
[I > 2 (I)] c
R1 = 0.0475,
wR2 = 0.1170
R1 = 0.0593,
R1 = 0.0334,
wR2 = 0.0864
R1 = 0.0362,
R indices (all data) c
wR2 = 0.1233
1.104 and –0.677
wR2 = 0.0884
0.402 and –0.313
Largest diff. peak and
hole (e·A–3)
2
2
2
2
aRint = Σ│Fo –Fo (mean)│/ΣFo , where Fo (mean) is the average intensity of symmetry equivalent diffractions.
2
c
bS = [Σw(Fo – Fc2)2]/(n – p)1/2, where n = number of reflections, p = number of parameters. R = [Σ(||Fo| –
2
4
|Fc|)/Σ|Fo|); wR = [Σ(w(Fo – Fc2)2)/Σ(wFo )]1/2.
Results and Discussion
Synthesis
Treatment of the thiocarbonato complexes of iron (1-4) with EPh3 under photolytic
conditions produced the mono-substituted complexes in moderate yields (Scheme 1). For the
di- (3: Y= S) and tri-thiocarbonato complexes (4: Y= Y'= S) small amounts of the chelated
complexes (9, 10) were obtained from these reactions (Scheme 1). They have been identified
by their spectroscopic techniques and compared to the reported values [26,27]. Treatment of
the chelated complexes with EPh3, either photolytically or thermally, did not lead to the
substituted products 5-8, only decomposition of the reactants are observed.

The brown-red complexes (5-8) are stable solids and are soluble in common organic solvents.
1
31
They have been characterized by UV-Vis, IR, H-, P-NMR spectral data and by elemental
analysis. The IR spectra of 5 and 6 showed only one strong band for the terminal carbonyl
ligand in the ranges of 1924-1963 cm-1, while that of 7 and 8 are in the ranges1946-1942 cm-1,
1941-1923 cm-1, respectively. These ranges are lower than those reported for the parent
thiocarbonates [25-27] which might be due to weaker –acceptor properties of the ER3
compared to that of CO ligand. The stretching frequency of the terminal carbonyl group of
these three families of complexes decreased on going from the PPh3 to AsPh3 to SbPh3
substituted complexes. This may be due to increase of the electron density on the metal
center in accordance to the σ–donating and π-accepting ability of the EPh3 ligands. In terms
of changing the thiocarbonato ligands, the CO frequency decreases from the mono- to di- to
trithiocarbonato ligands for the same EPh3 ligand. This might be due to the weaker electron
withdrawing ability of the S atom compared to that of O atom, which resulted in a higher
electron density on the iron atom in case of increasing the number of S atoms. The spectra of
5 and 6 show the ketonic CO-group of the thiocarbonato ligand in the range of 1666–1674 cm-
1
which decreases on going from PPh3 to SbPh3. This peak is absent from the spectra of 7
and 8 which is replaced by the C=S frequency in the range of 1589-1494 cm-1 which also
depends on the EPh3 ligand as shown for complexes 5 and 6.

The cyclopentadienyl ligand protons of complexes 5 – 8 appeared in the 1H-NMR spectra
of these complexes as one singlet in the ranges of 4.51-4.75 ppm. This range is lower than
that of dicarbonyl parents [26], which might be due to higher electron density around iron
resulting from the stronger –donor ability of the ER3 ligands. The Cp-chemical shifts of
these complexes change with substitution in the order PPh3 < AsPh3 < SbPh3 derivatives for
the same thiocarbonato ligand. The aromatic protons of the EPh3 ligands and the
thiocarbonato phenyl ring are observed at the aromatic ranges. These chemical shifts are
31
similar to those observed for the analogous thiocarboxylato complexes [12]. The P-NMR
spectra of 5a-8a showed a singlet for the P-atom of the PPh3 ligand in the range of 77.5-68.0
ppm which are lower than those observed for the corresponding thiocarboxylate complexes
[12].
The UV-Vis. spectra of complexes 5 - 8 were measured in dichloromethane solution
and Figure 1 showed the UV-Vis spectrum of complexes 6b as a representative example. A
broad band in the range of 381-445 nm is observed in the spectra of 5 - 8 which may be
assigned to the Fe → Cp metal-ligand charge transfer (MLCT) transition [29]. The λmax for
these complexes is not very sensitive to the type of ER3 ligand [12,29].
Crystal structures of 1 and 5a
The molecular structures of 1 and 5a are shown in Figures 2 and 3 while selected bond
lengths and angles are summarized in Table 2. Three legged piano stool structures are
representation of these complexes with the Cp ring as their base. The average Fe-C(Cp) bond
distance of 1 is with 2.091(6) Å comparable to that reported for related systems [25-27] as
well as to that of 5a (2.094(7) Å). The FeCO bond distances of 1 (1.782(3), 1.787(3) Å) are
longer than that of 5a (1.747(4) Å) in consistence with the IR-data. The Fe–S bond distance
of 5a (2.2666(9) Å) is shorter than the corresponding distance of 1 (2.2763(6) Å). The FeP
bond distance of 5a (2.2066(9) Å) is shorter than that of CpFe(CO(PPh3)SCO(2-C4H3S) of
2.2284(9) Å [31]. The ketonic CO bond lengths of the thiocarbonato ligand of 1 (1.192(3) Å)
and of 5a (1.190(4) Å) are comparable to each other and to those found in analogous
complexes [25-27]. The angles around the iron center of 1 and 5a are around 90º showing
disordered octahedral geometry. The FeSCO angles (1: 106.80(2)º, 5a: 104.67(12)º) are
consistent with an sp3 hybridized S atom. The S-C=O, O-C=O and S-C-O angles of the

thiocarbonato ligand in both 1 and 5a (Table 2) are close to 120º indicating the planarity of
this moiety.
Table 2: Selected bond lengths (Å) and angles (°) of CpFe(CO)2SCO2-2-C6H4Cl, 1 and
CpFe(CO)(PPh3)SCO2-2-C6H4Cl, 5a
1b)
5a
Fe1–C1
Fe1–C2
Fe1–C3
Fe1–C4
Fe1–C5
Fe1–C6
Fe1–P1
Fe1–S3
C7–O2
2.081(3)
2.074(3)
2.107(3)
2.113(3)
2.095(3)
1.747(4)
2.2066(9)
2.2666(9)
1.190(4)
Fe1–C1
Fe1–C2
Fe1–C3
Fe1–C4
Fe1–C5
Fe1–C6
Fe1–C7
Fe1–S1
C8–O3
2.111(2)
2.085(3)
2.071(3)
2.081(3)
2.106(2)
1.782(3)
1.787(3)
2.2763(6)
1.192(3)
Fe1–D1a)
1.721(2)
Fe1–D1
1.715(1)
C6–Fe1–P1
C6–Fe1–S3
94.86(11)
92.46(11)
C6–Fe1–C7
C6–Fe1–S1
94.03(12)
92.57(8)
P1–Fe1–S3
C7–S3–Fe1
O2–C7–O3
91.31(3)
104.67(12)
120.7(3)
C7–Fe1–S1
C8–S1–Fe1
O3–C8–O4
93.96(7)
106.82(8)
120.3(3)
O2–C7–S3
O3–C7–S3
130.3(3)
109.0(2)
O3–C8–S1
O4–C8–S1
129.69(19)
108.7(3)
a) D1 denotes the geometrical centroids of C5H5 groups. b) For the disordered fragments of 1 only
bond angles of fragment are given.
Conclusion
The substitution reactions of the thiocarbonato complexes of iron resulted in the formation of
the mono-substituted complexes. The substitution of CO ligand by EPh3 group in these
complexes resulted in increasing the electron density around the iron atom in the order PPh3
< AsPh3 < SbPh3. This is observed in the stretching frequency of the terminal carbonyl group
in the IR spectra, the position of the Cp-protons in the 1H-NMR spectra and by shortening of
the Fe-CO bond length as observed in the X-ray crystal structure determination.
Supporting Information available: Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication, CCDC-1545317 for
5a, and CCDC-1545318 for 1. Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [E- mail:
deposit@ccdc.cam.ac.uk].

Acknowledgements
M.E. thanks the Deanship of Research, Jordan University of Science and Technology
for financial support Grant No. 105/2016.
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Figure 1: UV-Vis spectrum of CpFe(CO)(AsPh3)SCO2-4-C6H4Cl, 6b in CH2Cl2

Figure 2: ORTEP (30 % ellipsoid probability) of the molecular structure of
CpFe(CO)(PPh3)SCO2-2-C6H4Cl (5a).

Figure 3: ORTEP (30 % ellipsoid probability) of the molecular structure of
CpFe(CO)2SCO2-2-C6H4Cl (1). Of disordered atoms only one atomic position is shown.

Substitution Reactions of Mono-, Di- and Tri-thiocarbonato
Complexes of Iron
M. El-khateeb, A. Mansor, I. Jibril, T. Rüffer, H. Lang
Monosubstituted complexes of the general formula CpFe(CO)(EPh3)SC(Y)Y'R [Y= Y'= O; R= 2-
C6H4Cl (5), 4-C6H4Cl (6). Y= S, Y'= O; R= C6H4F (7), Y= Y' = S; R= Ph (8). E= P (a), As (b), Sb (c)]
1
have been isolated and characterized by spectroscopic analysis (UV-Vis, IR, H-, 31P-NMR)
and elemental analysis. The molecular structures of CpFe(CO)(PPh3)SCO2-2-C6H4Cl (5a) and
its dicarbonyl parent CpFe(CO)2SCO2-2-C6H4Cl (1) have been determined by X-ray
crystallography.