Synthesis, characterization and electrochemical behavior of unsymmetric transition metal-terminated biphenyl ethynyl thiols

Article abstract of DOI:10.1016/j.jorganchem.2006.12.002

The synthesis of the biphenyl alkynyl thiols and thioesters R′-C{triple bond, long}C-C₆H₄-C₆H₄-SR (3: R′ = SiMe₃, R = C(O)Me; 4: R′ = SiMe₃, R = H; 5: R′ = H, R = C(O)Me) from I-C₆H₄-C₆H₄-SC(O)Me (1) is described. Molecules 1 and 5 have been used as starting materials in the synthesis of mono- and heterobimetallic transition metal complexes of type L_nM′-C{triple bond, long}C-C₆H₄-C₆H₄-SR (7: L_nM′ = Fc, R = C(O)Me; 8: L_nM′ = Fc, R = H; 10: L_nM′ = (Ph₃P)Au, R = C(O)Me; 14: L_nM′ = FcPPh₂-Au, R = C(O)Me; Fc = (η⁵-C₅H₅)(η⁵-C₅H₄)Fe; FcPPh₂ = (η⁵-C₅H₅)(η⁵-C₅H₄PPh₂)Fe). While complex 7is accessible by the Sonogashira cross-coupling of Fc-C{triple bond, long}CH (6) with 1, molecules 10 and 14 can be prepared by treatment of the thioester 5 with (Ph₃P)AuCl (9) and FcPPh₂-AuCl (13), respectively. The molecular solid state structures of 3, 7, 10 and 13-15 have been determined by single crystal X-ray crystallographic analysis. Typical features of these species are their linear M-C{triple bond, long}C-C₆H₄-C₆H₄-SR structure and the lack of coplanarity of the biphenyl arene rings. The overall length of these complexes are 13.345(2) A? for 3 (molecule A), 15.146(3) A? for 7, 15.705(2) A? for 10 (molecule A) and 15.649(4) A? for 14. The thioester groups are pointing away from the ferrocene building block. In 7 a linear 1D chain is set-up by π-interactions between two independent molecules of 7. Characteristic for 15 is the formation of a Au₂I₂ ring, while 13 is monomeric. All compounds were studied with cyclic voltammetry. Characteristic are the reversible ferrocene Fe(II)/Fe(III) redox wave, the irreversible reduction of Au(I) to Au(0), the oxidative cleavage of the S-C(O)Me sulfur-carbon (3, 5, 7, 10 and 14) and of the sulfur-hydrogen bond (4 and 8), respectively. Electronic effects extending from the -SH-end group to the ferrocene unit resulting in considerable shifts of the redox potential of the latter entity are found. Coordination of Au(I) at the FcPPh₂ moiety also results in a shift of the redox potential of the ferrocene group indicative of an electron withdrawing effect of the Au(I) species.

Full text of DOI:10.1016/j.jorganchem.2006.12.002

Journal of Organometallic Chemistry 692 (2007) 1530–1545
www.elsevier.com/locate/jorganchem
Synthesis, characterization and electrochemical behavior of
unsymmetric transition metal-terminated biphenyl ethynyl thiols
a
a
a
a
b
Katrin Ro¨ßler , Tobias Ruffer , Bernhard Walfort , Rico Packheiser , Rudolf Holze ,
¨
c
a,
*
Michael Zharnikov , Heinrich Lang
a
Technische Universita¨t Chemnitz, Fakulta¨t fu¨r Naturwissenschaften, Institut fu¨r Chemie, Lehrstuhl fu¨r Anorganische Chemie,
Straße der Nationen 62, 09111 Chemnitz, Germany
b
Technische Universita¨t Chemnitz, Fakulta¨t fu¨r Naturwissenschaften, Institut fu¨r Chemie, AG Elektrochemie,
Straße der Nationen 62, 09111 Chemnitz, Germany
Universita¨t Heidelberg, Institut fu¨r Angewandte Physikalische Chemie, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany
c
Received 30 August 2006; received in revised form 30 November 2006; accepted 5 December 2006
Available online 8 December 2006
Abstract
The synthesis of the biphenyl alkynyl thiols and thioesters R0–C„C–C6H4–C6H4–SR (3: R0 = SiMe3, R = C(O)Me; 4: R0 = SiMe3,
R = H; 5: R0 = H, R = C(O)Me) from I–C6H4–C6H4–SC(O)Me (1) is described. Molecules 1 and 5 have been used as starting materials
in the synthesis of mono- and heterobimetallic transition metal complexes of type LnM0–C„C–C6H4–C6H4–SR (7: LnM0 = Fc,
R = C(O)Me; 8: LnM0 = Fc, R = H; 10: LnM0 = (Ph3P)Au, R = C(O)Me; 14: LnM0 = FcPPh2-Au, R = C(O)Me; Fc = (g5-C5H5)(g5-
C5H4)Fe; FcPPh2 = (g5-C5H5)(g5-C5H4PPh2)Fe). While complex 7is accessible by the Sonogashira cross-coupling of Fc–C„CH (6)
with 1, molecules 10 and 14 can be prepared by treatment of the thioester 5 with (Ph3P)AuCl (9) and FcPPh2-AuCl (13), respectively.
The molecular solid state structures of 3, 7, 10 and 13–15 have been determined by single crystal X-ray crystallographic analysis. Typ-
ical features of these species are their linear M-C„C–C6H4–C6H4–SR structure and the lack of coplanarity of the biphenyl arene rings.
˚
˚
˚
The overall length of these complexes are 13.345(2) A for 3 (molecule A), 15.146(3) A for 7, 15.705(2) A for 10 (molecule A) and
˚
15.649(4) A for 14. The thioester groups are pointing away from the ferrocene building block. In 7 a linear 1D chain is set-up by p-inter-
actions between two independent molecules of 7. Characteristic for 15 is the formation of a Au2I2 ring, while 13 is monomeric.
All compounds were studied with cyclic voltammetry. Characteristic are the reversible ferrocene Fe(II)/Fe(III) redox wave, the irre-
versible reduction of Au(I) to Au(0), the oxidative cleavage of the S–C(O)Me sulfur–carbon (3, 5, 7, 10 and 14) and of the sulfur–hydro-
gen bond (4 and 8), respectively. Electronic effects extending from the –SH-end group to the ferrocene unit resulting in considerable shifts
of the redox potential of the latter entity are found. Coordination of Au(I) at the FcPPh2 moiety also results in a shift of the redox poten-
tial of the ferrocene group indicative of an electron withdrawing effect of the Au(I) species.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ferrocene; Gold; Thiol; Thioester; Biphenyl; Alkyne; X-ray structure; Cyclic voltammetry
1. Introduction
the preparation of the respective systems is molecular self-
assembly, involving the functionalization of the relevant
substrate by the so-called self-assembled monolayers
(SAMs) [2,3,11], which are 2D polycrystalline films of
semi-rigid molecules that are chemically anchored to the
substrate. A large advantage of these systems is a flexible
molecular architecture of the SAM constituents, which gen-
erally consist of three essential parts: a head group that
binds strongly to the substrate, a tail group that constitutes
The fabrication of electrochemically and catalytically
active surfaces and 2D templates is an important challenge
from both, scientific viewpoint and in view of possible prac-
tical applications [1]. A promising bottom-up approach for
*
Corresponding author. Tel.: +49 371 531 21210; fax: +49 371 531 21219.
E-mail address: heinrich.lang@chemie.tu-chemnitz.de (H. Lang).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.12.002

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1531
the outer surface of the film, and a spacer that separates
head and tail groups. Within this general framework, one
can combine different moieties and functional groups to a
simple rod-like molecule, a complex assembly, or even a
molecular device, which carry an active element, connected
to the substrate over the spacer and headgroup. As such
active element, different functional groups can be used,
including molecular switches, rectifying optically active
moieties, redox complexes, etc. Among other possibilities,
promising active elements are ferrocenes, which are very
robust compounds and excellent organometallic one-elec-
tron reservoirs [4]. In the entire molecular device, the ferro-
cene unit should be electrically connected to the substrate
by a suitable molecular spacer, which should possess a pos-
sibly high electric conductivity. In this regard, a oligophenyl
or phenylene–ethenylene chain is the best choice, consider-
ing that these moieties have much lower resistance as com-
pared to the aliphatic chain frequently used in the SAM
design [5,6]. In addition, the headgroup is of importance,
since the contact resistance of the molecule to the substrate
depends strongly on its bonding [7,8]. In this regard, a thiol
derivative headgroup is a good choice, since the respective
anchor has a high affinity to many metal and semiconductor
surfaces and is characterized by a quite low contact resis-
tance [7,8]. Another argument in favor of the thiol deriva-
tives is the fact that thiol-derived SAMs are the most
frequently studied SAM systems at present, available results
include analysis of their structure, thermodynamics and
kinetics of their formation, and design of application-rele-
vant systems [3,9–12]. Next to x-functionalized alkanethi-
ols, also organometallic thiols and thioesters based on
ferrocene have been studied in detail [12,13].
organic and/or inorganic bridges [14]. Based on these
studies, we focused recently our attention on the synthe-
sis of unsymmetric biphenyl-thiol- and -thioester-func-
tionalized ferrocenes, because this permits systematic
modification and, hence, studies of the nature of interfa-
cial barriers to gain a more universal structure-relation-
ship how structural effects can mediate electron transfer
[15].
Herein, we report on an efficient synthesis of biphenyl
ethynyl terminated thioesters. A general synthetic scheme
for the preparation of mono- and heterobimetallic ferro-
cene and/or triphenylphosphine gold biphenyl ethynyl thi-
oesters and their transformation to the appropriate thiols is
discussed as well. In addition, the electrochemical redox
and solid state properties of the latter molecules will be
presented.
2. Results and discussion
As shown in Scheme 1, the thio-acetyl molecule Me3Si–
C„C–C6H4–C6H4–SC(O)Me (3) can be synthesized in a
straightforward manner through the palladium–copper
catalyzed Sonogashira cross-coupling of I–C6H4–C6H4–
SC(O)Me (1) with Me3SiC„CH (2). Compound 3 can be
converted to Me3Si–C„C–C6H4–C6H4–SH (4) by its con-
secutive reaction with NH4OH and HCl in tetrahydrofuran
as solvent at room temperature (Scheme 1). When 3 is trea-
ted with [nBu4N]F in a ratio of 1:2.5 and a proton source is
added, then HC„C–C6H4–C6H4–SC(O)Me (5) is accessi-
ble (Scheme 1).
Compounds 3–5 were characterized by elemental analy-
sis, NMR (1H, 13C{1H}, 29Si{1H}) and IR spectroscopy.
The exchange of the Me3Si and the C(O)Me groups in 3 with
hydrogen to give 4 and 5 is indicated by very prominent res-
onance signals and vibrations, which allow to monitor the
Recently, we used functionalized ferrocenes in the syn-
thesis of multi(hetero)metallic complexes in which the
different transition metals are connected by p-conjugated
Me3SiC CH
[(Ph3P)2PdCl2/CuI], NEtiPr2
(2)
I
SAc
Me3SiC
C
SAc
1
3
1. NH4OH, 2. HCl
Thf
C
C
SH
Me3Si
4
Me3SiC
C
SAc
3
[nBu4N]F, H+
Thf
HC
C
SAc
5
Scheme 1. Synthesis of 3–5 (Ac = C(O)Me).

1532
K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
Fig. 1. ORTEP plot (50% probability level) of the three crystallographically independent molecules of 3 (3A–3C) with the atom numbering scheme. The
orientations shown for 3A–3C are related to their arrangement in the asymmetric unit.
progress of the appropriate reaction by NMR and IR spec-
troscopy (Section 3).
rotamere of 3A–3C exists in the solid state. The difference
of the dihedral angles in 3A–3C can most likely be
explained by packing effects (see Table 2).
Single crystals of 3 suitable for X-ray diffraction studies
could be grown from a saturated dichloromethane solution
at 25 ꢁC. The molecular structure of 3 is shown in Fig. 1.
ꢀ
Compound 3 crystallizes in the triclinic space group P1
Table 2
with the three crystallographically independent molecules
a
˚
Selected bond distances (A) and bond angles (ꢁ) for 7
3A–3C within the asymmetric unit. Selected bond distances
Bond distances
˚
(A) and bond angles (ꢁ) are summarized in Table 1. Crys-
C6–C11
C16–C19
C25–O1
Fe1–D2b
1.430(3) C11–C12 1.193(3) C12–C13
1.440(3)
1.795(3)
1.648(1)
tallographic and refinement data are given in Section 3
(Table 6).
1.484(3) C22–S1
1.776(2) S1–C25
1.196(3) C25–C26 1.500(3) Fe1–D1b
1.645(1)
Related bond lengths of 3A–3C are equivalent within
their standard deviations, while bond angles of 3A–3C
show some differences (Table 1). The major difference
between 3A and 3C are the dihedral angles of the biphenyl
units being 26.8(2)ꢁ for 3A (C6–C11 vs. C12–C17), 22.8(2)ꢁ
for 3B (C25–C30 vs. C31–C36) and 36.2(1)ꢁ for 3C (C44–
C49 vs. C50–C55). This indicates that no favorable
Bond angles
C6–C11–C12 178.2(3)
C11–C12–C13
179.6(3)
C22–S1–C25
100.43(11)
a
Standard uncertainties of the last significant digit(s) are shown in
parenthesis.
b
D1 = centroid of C5H5, D2 = centroid of C5H4.
Table 1
Selected bond distances (A) and bond angles (ꢁ) for the three independent molecules of 3
a
˚
3A
3B
3C
Bond distances
Si1–C4
C4–C5
1.846(4)
1.204(5)
1.437(5)
1.490(5)
1.771(4)
1.771(5)
1.194(6)
1.515(6)
13.345(2)
Si2–C23
C23–C24
C24–C25
C28–C31
C34–S2
S2–C37
C37–O2
C37–C38
Si2–S2
1.843 (4)
1.203(5)
1.438(5)
1.497(4)
1.770(3)
1.789(4)
1.197(5)
1.502(5)
13.347(2)
Si3–C42
C42–C43
C43–C44
C47–C50
C53–S3
S3–C56
C56–O3
C56–C57
Si3–S3
1.840 (4)
1.197 (5)
1.440(5)
1.489(5)
1.772(3)
1.785(4)
1.198(4)
1.503(5)
13.310(2)
C5–C6
C9–C12
C15–S1
S1–C18
C18–O1
C18–C19
Si1–S1
Bond angles
Si1–C4–C5
C4–C5–C6
C15–S1–C18
a
176.8(4)
179.4(4)
104.01(19)
Si2–C23–C24
C23–C24–C25
C34–S2–C37
175.5(4)
178.8(4)
104.10(17)
Si3–C42–C43
C42–C43–C44
C53–S3–C56
175.2(3)
178.0 (4)
102.33(16)
Standard uncertainties of the last significant digit(s) are shown in parenthesis.

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1533
˚
Fig. 2. Graphical representation of the p–p-interaction (C7–C7A) between pairs of 3A (d(C7–C7A) = 3.313 A).
Within the asymmetric unit no p–p-interactions between
molecules 3A–3C exist. However, such a structural motif is
found for a pair of two molecules of 3A as given by the dis-
The thio acetyl derivatives 1 and 5 are particularly well
suited to prepare the ferrocene and triphenylphosphine
gold complexes 7, 10 and 14 as shown in Eq. (1) and
Schemes 2 and 3, respectively.
˚
tance of 3.313 A between C7 and C7A, respectively, which
is remarkable short (Fig. 2) [16].
All other bond distances and angles of 3 agree well with
those reported for similar molecules [17]. Finally, the over-
Carbon–carbon cross-coupling catalyzed by transition
metals can successfully be used to prepare linear Fc–C„
C–C6H4–C6H4–SC(O)Me (7) (Fc = (g5-C5H5)(g5-C5H4)Fe)
(Scheme 2). In this respect, I–C6H4–C6H4–SC(O)Me (1)
was reacted with FcC„CH (6) in presence of catalytic
amounts of [(Ph3P)2PdCl2/CuI] in triethylamine as solvent
˚
all length of a single molecule of 3 is 13.345(2) A for 3A,
˚
˚
13.347(2) A for 3B and 13.310(2) A for 3C as calculated
between Si(1,2,3) and S(1,2,3) (Fig. 1).
C C H
SAc
C C
[(Ph3P)2PdCl2/CuI]
NEt3
Fe
Fe
+
I
SAc
1
6
7
C C
SH
1. NH4OH, 2. HCl
Thf
Fe
8
Scheme 2. Synthesis of 7 and 8.
AuCl
PPh2
PPh2
(tht)AuCl (12)
Fe
Fe
-tht
11
13
Au
AuI
C
C
SAc
PPh2
PPh2
5
+
+
Fe
Fe
. . .
[CuI], NEt3
14
15
Scheme 3. Synthesis of 14 by reacting 13 with 5 (Ac = C(O)Me, tht = tetrahydrothiophene).

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K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
following the Sonogashira cross coupling protocol (Scheme
2) [18]. After appropriate work-up, complex 7 could be iso-
lated as an orange solid in 83% yield. The S-acetyl group in
7 can successfully be converted to a SH moiety by the sub-
sequent reaction of 7 with NH4OH and HCl under similar
reaction conditions as described for the synthesis of 4 (vide
supra).
two independent molecules of 7. Respecting this structural
mode it finally leads to the 1D chain formation of 7.
A further possibility to introduce a thio-acetyl or thiol-
containing group in organometallic chemistry is outlined in
Eq. (1) and Scheme 3 and involves the reaction of a
phosphino gold(I) chloride entity with the alkyne
HC„C–C6H4–C6H4–SC(O)Me (5). The gold acetylide
(Ph3P)Au-C„C–C6H4–C6H4-SC(O)Me (10) was prepared
basically in accordance with the method reported by Vice-
nte et al., i.e., treatment of 5 with (Ph3P)AuCl (9) in trieth-
ylamine as solvent [20]. It should be mentioned that this
reaction requires the addition of catalytic amounts of
[CuI] to obtain colorless 10 in high yield [21].
In order to obtain structural parameters that might be of
interest in the investigation of SAMs derived from such
complexes we carried out a single X-ray structure analysis
of 7. Orange single crystals could be obtained by slow
evaporation of a diethyl ether solution containing 7 at
5 ꢁC. Geometric details are listed in Fig. 3 and experimen-
tal crystal data in Table 6 (Section 3).
Compound 7 is set-up by the sandwich unit (g5-
C5H5)(g5-C5H4)Fe and the biphenyl ethynyl moiety
C„C–C6H4–C6H4–SC(O)Me (Fig. 3). The carbon–carbon
triple bond involved in connecting together the organome-
HC C
SAc
5
˚
(9)
(Ph3P)AuCl
tallic and organic entities is 1.193(3) A (C11–C12) which is
(Ph3P)Au C C
SAc
typical for this type of bonding [19]. The two cyclopenta-
dienyl rings are nearly parallel oriented to each other
(1.9(2)ꢁ) with D1–Fe–D2 separations being 1.648(1) and
[CuI], NEt3
10
ð1Þ
˚
1.645(1) A (D1 = centroid of the cyclopentadienyl ring
C5H5, D2 = centroid of the cyclopentadienyl ring C5H4).
As shown in Fig. 3, the aromatic rings defined by C13–
C18 and C19–C24 are rotated by 19.6(1)ꢁ and 14.0(1)ꢁ,
respectively, into opposite directions of the cyclopentadie-
nyl unit C6–C10. The dihedral angle of C13–C18 and
C19–C24 is 33.0(1) ꢁ assuming that in 7 the two biphenyl
arene rings are free to rotate as already discussed for 3
(vide supra). The thio-acetyl group is pointing to the oppo-
site site of the ferrocenyl sandwich entity. The overall
A similar synthesis procedure can be used for the prep-
aration of heterobimetallic FcPh2P–Au–C„C–C6H4–
C6H4–SC(O)Me (14) by reacting FcPh2P–AuCl (13) with
5 in a 1:1 molar ratio as depicted in Scheme 3. After appro-
priate work-up, complex 14 could be isolated in 53% yield.
Within the reaction of 5 with 13 heterobimetallic
FcPh2P–AuI (15) is formed as side product in 3% yield.
It could be separated from 14 by column chromatography
(Section 3). An explanation for the formation of 15 is given
by the halide exchange reaction between [CuI] and FcPh2P-
AuCl (13), respectively.
All synthesized compounds are colorless (3–5 and 10),
yellow (13, 14 and 15) or orange (7 and 8) crystalline mate-
rials that could be purified by conventional column chro-
matography (Section 3). They nicely dissolve in common
organic polar solvents such as dichloromethane and tetra-
hydrofuran. All compounds are stable toward moisture
˚
˚
length of 7 is with 15.146(3) A and 15.149(3) A, respec-
tively, as calculated from C8 and C9 to the sulfur atom
˚
S1 by 1.81 A longer as found for 3 (Fig. 1). Furthermore,
7 forms in the solid state a 1D-chain set-up by p-interac-
tions (Fig. 4). Significant p-contacts are observed between
˚
˚
C6A–C23B (3.587 A), C7A–C23B (3.468 A), C7A-C24B
˚
˚
(3.467 A), C8A–C24B (3.369 A) and C9A–C19B
(3.603 A), whereby the suffixes A and B correspond to
˚
Fig. 3. ORTEP plot (50% probability level) of 7 with the atom numbering scheme.

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1535
Fig. 4. Schematic view of the 1D chain function of 7.
and air, except the SH-terminated species 4 and 8. These
compounds, both in the solid state and in solution, are
all prone to oxidation (in solution more rapidly) to the cor-
responding disulfides. However, in deoxygenated and dried
solvents they are stable and can be kept for months without
decomposition.
state structures of these species are shown in Figs. 5–9,
the crystallographic data are summarized in Tables 6 and
7 (Section 3). From Figs. 5 to 9 it can be seen that the struc-
tures of 10 and 14 as well as 13 and 15 are essentially sim-
ilar as far as the molecule backbone is concerned.
Mononuclear 10 crystallizes in the triclinic space group
P1 with two molecules in the asymmetric unit (10A, 10B),
1
Analytic and spectroscopic (IR, H, 13C{1H}, 31P{1H},
ꢀ
29Si{1H} NMR, ESI-TOF MS) analyses of 3–5, 7, 8, 10
and 13–15 support their structural formulation as biphenyl
ethynyl thiols and unsymmetric transition metal-termi-
nated biphenyl ethynyl thiols (vide supra).
while heterobimetallic 14 crystallizes in the monoclinic
space group P2(1)/c (Fig. 5: 10, Fig. 6: 14). In addition
complex 14 exhibits a disorder of its terminal C6H4–
SC(O)Me groups with occupation factors of 0.58 and
˚
Structural information concerning the presence of the
thioesters and thiol moieties in 3–5, 7, 8, 10 and 14 was
obtained from the IR spectra (Section 3). Most informative
are the C„C, C@O and SH vibrations. For the HC„C
unit an absorption band is found at 2103 cmꢀ1, while the
Me3Si–C„C and LnM–C„C building blocks show their
C„C stretching frequencies between 2100 and
2200 cmꢀ1. The acetyl group in 3, 5, 7, 10 and 14 gives rise
to a very characteristic band at ca. 1700 cmꢀ1, while the SH
0.42. Selected bond lengths (A) and bond angles (ꢁ) are
given in Table 3 (10) and Table 4 (14).
Compounds 10 and 14 represent the first synthesized
and structurally characterized transition metal complexes
of type M–C„C–C6H4–C6H4–SR (R = H, alkyl, aryl,
C(O)Me, etc.), while complexes of structural type M–
C„C–C6H4–SR [22] and M–C6H4–C6H4–SR [23] are
already described.
Most characteristic for 10 and 14 is their almost linear
P–Au–C„C–C arrangement (10A: P1–Au1–C1 (177.0
(3)ꢁ), Au1–C1–C2 (177.0(3)ꢁ), C1–C2–C3 (176.3(4)ꢁ);
10B: P2–Au2–C35 (177.69(10)ꢁ), Au2-C35-C36 (177.4
(3)ꢁ), C35–C36–C37 (178.3(4)ꢁ); 14: P1–Au1–C23 (177.9
(2)ꢁ), Au1–C23–C24 (170.9(7)ꢁ), C23–C24–C25 (175.2
(8)ꢁ)) (Tables 3 and 4) and the lack of coplanarity of the
biphenyl arene rings (Figs. 5 and 6). These structural fea-
tures are similar to related species, i.e. M–C„C–C6H4–
SR [22] and M–C6H4–C6H4–SR [23].
vibration in 4 and 8 is found at ca. 2560 cmꢀ1
.
The 31P{1H} NMR spectra are most informative in
terms of the coordination mode of the phosphine groups
or the exchange of the gold-bonded chloride in 9 and 13
by an acetylide moiety. A deshielding of the phosphorus
atom in 11 is observed, when this unit is datively-bonded
to a AuCl and Au–C„C–C6H4–C6H4–SC(O)Me moiety,
respectively, i.e., 11: ꢀ17.52 ppm, 13: 27.6 ppm, 14:
36.4 ppm.
The 1H and 13C{1H} NMR spectra of the newly synthe-
sized compounds are also conclusive, especially the C„C,
C(O)Me, C5H5 and C5H4 groups (Section 3).
Additionally, the molecular structures of 10, 13, 14 and
15 were determined by single X-ray diffraction. The solid
The ferrocenyl group in 14 with Fe1–D1 and Fe1–D2
˚
separations of 1.640(3) and 1.634(3) A, respectively, exhib-
its a nearly coplanar conformation of the cyclopentadienyl
rings. The dihedral angle of the calculated mean plans of
the cyclopentadienyl rings is 3.5(6)ꢁ.

1536
K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
Fig. 5. The molecular structures (ORTEP plot, 50% probability level) of the two crystallographically independent molecules of 10 (10A: above, 10B:
below) with the atom numbering scheme. Hydrogen atoms are omitted for clarity. The orientation of 10A and 10B does not reflect their orientation within
the asymmetric unit.
Fig. 6. The molecular structure of 14 (ORTEP plot, 50% probability level) with the atom numbering scheme. Only one position of the disordered terminal
C6H4–SC(O)Me group is shown.
˚
For 14 unusual short intermolecular contacts between
C29–C30A, C30–C30A, C30–C29A, C26A–C34B, C27A–
C35B and C27A–C34B are observed in the solid state
(Fig. 7). For 10 a similar trend is recognized, which most
probably is originated from packing effects. Additionally,
significant p-interactions are found for 14 as shown in
Fig. 7. A 1D chain is formed by repeating sets of three mol-
lengths (A) and angles (ꢁ) are given in Table 5. Although
the molecular structures of 13 and 15 are very similar, both
complexes are not iso-structural. The reason therefore is
the formation of Auꢁ ꢁ ꢁI contacts between two molecules
˚
of 15 (d(Auꢁ ꢁ ꢁI) = 3.817 A) (Fig. 9). A similar behavior
5
˚
was found in (g -C5H4PPh2-AuI)2Fe (d(Auꢁ ꢁ ꢁI) = 3.909 A)
as well as in its chloride derivative [24] (see Table 7).
˚
ecules of 14. The overall length of 10 and 14 is 15.705(2) A
The AuÆI interactions in 15 are very weak, as the sum of
˚
˚
˚
(P1–S1) for 10A, 15.750(2) A (P2–S2) for 10B, 15.649(4) A
the van der Waals radii of Au and I amounts to 3.65–3.82 A
0
˚
(P1–S1) and 15.751(5) A (P1–S1 ) for 14.
[25]. In the case of (g5-C5H4PPh2-AuI)2Fe it is question-
able, whether an interaction can be discussed or not, how-
ever, the non-isostructurality of (g5-C5H4PPh2-AuI)2Fe
The molecular solid state structures of FcPPh2-AuX (13:
X = Cl, 15: X = I) are shown in Fig. 8, selected bond

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1537
˚
Fig. 7. p-Interactions between a set of three molecules of 14. Only the PhSAc unit with the major occupation is considered. d(C29–C30A) = 3.435 A,
˚
˚
˚
˚
˚
d(C30–C30A) = 3.590 A, d(C30–C29A) = 3.435 A, d(C26A–C34B) = 3.578 A, d(C27A–C35B) = 3.584 A, d(C27A–C34B) = 3.594 A.
Fig. 8. ORTEP plot (50% probability level) of the asymmetric unit of 13 (left) and 15 (right) with the atom numbering scheme.
vs. (g5-C5H4PPh2-AuCl)2Fe indicates a very weak Auꢁ ꢁ ꢁI
contact, too. Further ((RR0R00)P)AuI compounds which
show intermolecular Auꢁ ꢁ ꢁI contacts are not described so
far. Complexes of this type were either found to be mono-
meric (e.g. R = R0 = R00 = Ph [26], 2,4,6-Me3C6H2 [27]) or
exhibiting Au–Au contacts (e.g. R = R0 = Me, R00 = Ph
[28]).
nearly ecliptic conformation is observed, whereas the
respective rings in 15 adopt a staggered conformation. In
both cases the cyclopentadienyl rings are nearly parallel
oriented to each other, as expressed by their interplanar
angles of the calculated mean planes (13: 1.4(8)ꢁ and 15:
2.4(3)ꢁ).
˚
The gold-halide distances are 2.280(2) A for 13 and
˚
Due to the formation of a Au2I2 4-membered ring in 15
the P1–Au1–I1 angle with 171.19(2)ꢁ deviates significantly
from linearity, when compared with the P1–Au1–Cl1 angle
(177.12(10)ꢁ) in 13. As observed for (g5-C5H4PPh2–
2.5758(3) A for 15. These values are in close agreement
with other phosphane–gold complexes featuring Au–Cl
or Au–I bonds [24,28,29].
All compounds were studied with cyclic voltammetry. In
positive going potential scans of 3 and 5 a current shoulder
in the onset of electrolyte solution oxidation is observed at
EFeC = 1.38 V for 3 and at EFeC = 1.35 V for 5 (Fig. 10); it
is assigned to removal of an electron from the sulfur atom
and subsequent cleavage of the S–C(O)Me sulfur–carbon
bond with formation of an acylium cation and a sulfonium
radical. Recombination of the latter species to a disulfide is
conceivable, a weak cathodic current wave in the negative
5
˚
AuCl)2Fe (d(P–Au) = 2.2262(13) A) and (g -C5H4PPh2–
˚
AuI)2Fe (d(P–Au) = 2.248(9)/2.240(8) A) [24], the P–Au
distances in 13 are significantly shorter, when compared
˚
with 15 (13: d(Au1–Pl) = 2.228(2) A vs. 15: d(Au1–
˚
P1) = 2.2542(9) A), which most probably can be explained
by the higher trans influence of the iodide vs. the chloride
ligand. A further structural feature of 13 vs. 15 is the differ-
ent conformation of the cyclopentadienyl rings. For 13 a

1538
K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
scattering it is not justified to speculate about electronic
effects of the molecules and the involved substituents on
the oxidation potential.
In case of –SH-terminated groups oxidation of the sul-
fur again resulting in the formation of a sulfonium radical
is observed at EFeC = 1.1 V (4) and EFeC = 1.24 V (8)
(Fig. 11).
Despite the rather similar inductive effects of the mole-
cules attached to the –SH-group oxidation is more difficult
(i.e. electron density at the –SH group is smaller) in the case
of 8.
A further building block shared by 7, 8, 13, 14 and 15 is
the ferrocene unit. This moiety can be employed to probe
electron density shifts in molecules caused by substituents
and intramolecular electronic communication. In a direct
comparison of 7 and 8 differing only in the sulfur-contain-
ing end-group the former shows a redox potential EFeC
=
0.18 V, the latter (8) EFeC = 0.04 V. Obviously oxidation
of 8 is easier, i.e. charge density at the ferrocene moiety is
higher. As already observed in Fig. 11, oxidation of the fer-
rocene unit in 8 and subsequent oxidation of the –SH group
results in a practically complete disappearance of the reduc-
tion wave of the ferrocene entity. This could only be
observed (with the result stated above) in narrow potential
scans around EFeC = 0.04 V. In case of 13 EFeC = 0.32 V,
14 EFeC = 0.29 V, and 15 E0 = 0.30 V were observed for
the ferrocene unit. The redox potentials of 14 and 15 are
very similar implying a dominant electron withdrawing
influence of the Au(I) species coordinated to the PPh2 unit
and an only slightly larger electron withdrawing effect of the
halides in 13 and 15. Reduction of this Au(I) species is
always irreversible, i.e., no reoxidation is observed. The
reduction appears as a wave on the cathodic decomposition
of the electrolyte system. The respective current waves are
observed at E = ꢀ2.59 V (10), E = ꢀ2.72 V (13), E =
ꢀ2.66 V (14, very weak) and E = ꢀ2.78 V (15). In case of
10 a Ph3P unit is coordinated to Au(I), in all other remain-
ing molecules a PPh2Fc unit is in this position. The poten-
tial difference of about 70 mV between the 10 and 14 (the
molecules differ only in this unit) implies, that only the
properties of the PX substituents have an effect on the gold
reduction potential. The halide substituents in 13 and 15
affect a further electron drag resulting in a negative shift
of the reduction potential, the shifts do not reflect the elec-
tronegativities of the halide elements.
˚
Fig. 9. Intermolecular Au2I2 ring formation in 15 (d(Auꢁ ꢁ ꢁI) = 3.817 A).
Table 3
a
˚
Selected bond distances (A) and bond angles (ꢁ) for 10
10A
10B
Bond distances
P1–C17
P1–C23
P1–C29
P1–Au1
Au1–C1
C1–C2
C2–C3
C6–C9
C12–S1
S1–C15
C15–C16
C15–O1
1.819(4)
1.819(4)
1.813(3)
2.2758(9)
2.009(4)
1.192(5)
1.445(5)
1.486(5)
1.776(4)
1.791(4)
1.515(5)
1.202(5)
P2–C51
P2–C57
P2–C63
P2–Au2
Au2–C35
C35–C36
C36–C37
C40–C43
C46–S2
1.816(4)
1.822(3)
1.821(4)
2.2733(9)
2.001(4)
1.199(5)
1.434(5)
1.485(5)
1.774(4)
1.686(7)
1.524(7)
1.235(6)
S2–C49
C49–C50
C49–O2
Bond angles
C17–P1–C23
C17–P1–C29
C17–P1–Au1
C23–P1–C29
C23–P1–Au1
C29–P1–Au1
P1–Au1–C1
Au1–C1–C2
C1–C2–C3
C12–S1–C15
a
105.91(18)
103.94(17)
115.96(13)
104.74(16)
110.71(12)
114.60(12)
177.12(10)
177.0(3)
C51–P2–C57
C51–P2–C63
C51–P2–Au2
C57–P2–C63
C57–P2–Au2
C63–P2–Au2
P2–Au2–C35
Au2–C35–C36
C35–C36–C37
C46–S2–C49
106.31(16)
106.63(17)
110.40(12)
104.20(16)
115.05(12)
113.60(12)
177.69(10)
177.4(3)
176.3(4)
101.67(18)
178.3(4)
107.7(2)
In this work, new linear biphenyl ethynyl thiol and thio
acetyl molecules were synthesized and characterized. Based
on these studies we used these molecules as starting mate-
rials for the preparation of mono- and heterobimetallic
complexes containing the C„C–C6H4–C6H4–SR (R = H,
C(O)Me) ligand by applying different synthesis strategies.
Standard uncertainties of the last significant digit(s) are shown in
parenthesis.
going scan observed with related molecules showing the
same oxidation behavior supports this assumption [15].
Respective oxidation potentials for the other com-
pounds are EFeC = 1.42 V (7), EFeC = 1.45 V (8),
EFeC = 1.42 V (10), EFeC = 1.45 V (14). Because in all cases
no well-defined peaks but only current shoulders are
observed and the assigned potentials show only a small
Complexes
LnM–C„C–C6H4–C6H4–SR
(LnM = Fc,
(Ph3P)Au, FcPPh2-Au); Fc = ((g5-C5H5)(g5-C5H4)Fe) are
rigid-rod structured. The electrochemical behavior of these
compounds, in particular the oxidation of the sulfur-con-
taining end-group, the irreversible reduction of the Au(I)
species and the redox behavior of the ferrocene unit can

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1539
Table 4
a
˚
Selected bond distances (A) and bond angles (ꢁ) for 14
Bond distances
P1–C6
1.784(7)
2.2737(15)
1.463(9)
1.707(15)
1.640(3)
P1–C11
1.813(7)
2.017(6)
1.512(9)
1.858(17)
1.634(3)b
P1–C17
C23–C24
C34–S1
1.819(6)
P1–Au1
C24–C25
S1–C37
Fe1–D1b
Au1–C23
C28–C31
C37–C38
Fe1–D2
1.172(9)
1.757(7)
1.244(17)
C37–O1
Bond angles
C6–P1–C11
C11–P1–C17
Au1–C23–C24
C34–S1–C37
a
105.7(3)
105.8(3)
170.9(7)
105.6(7)
C6–P1–C17
103.9(3)
P1–Au1–C23
C23–C24–C25
C340–S10–C370
177.9(2)
175.2(8)
104.4(8)
c
Standard uncertainties of the last significant digit(s) are shown in parenthesis.
D1 = centroid of C5H5, D2 = centroid of C5H4.
b
c
0
= disordered atoms.
Table 5
a
˚
Selected bond distances (A) and bond angles (ꢁ) for 13 (X = Cl) and 15 (X = I)
Bond distances
Bond angles
13
15
13
15
P1–Au1
P1–C6
P1–C11
P1–C17
Fe1–D1b
Fe1–D2b
Au1–X1
a
2.228(2)
1.781(8)
1.812(4)
1.823(5)
1.372(4)
1.630(4)
2.280(2)
2.2542(9)
1.782(3)
1.820(4)
1.824(4)
1.656(2)
1.649(2)
2.5758(3)
P1–Au1–X1
177.12(10)
112.6(3)
112.46(18)
115.3(2)
106.6(3)
104.1(3)
105.0(3)
171.19(2)
C6–P1–Au1
C11–P1–Au1
C17–P1–Au1
C6–P1–C11
C6–P1–C17
C11–P1–C17
118.93(11)
113.00(11)
109.69(11)
105.67(16)
104.62(16)
103.57(16)
Standard uncertainties of the last significant digit(s) are shown in parenthesis.
D1 = centroid of C5H5, D2 = centroid of C5H4.
b
be rationalized in terms of electron-donating and -with-
drawing properties of the various building blocks of the
investigated molecules. Preparation of self-assembled mono-
layers by applying the bottom-up approach of the synthe-
sized species is in progress [30].
H3PO4, d 0.00) and 29Si{1H} NMR spectra at 49.693 MHz
as external standard (relative to SiMe4, d 0.00) in CDCl3.
Cyclic voltammograms were recorded in a dried single-
compartment cell purged with purified argon at 25 ꢁC.
Platinum wires served as working and as counter elec-
trodes. A non-aqueous saturated calomel electrode served
as reference electrode. For ease of comparison, all poten-
tials are converted to the ferrocene–ferrocenium couple
Cp2Fe/Cp2Fe+ (Cp2Fe = (g5-C5H5)2Fe) as the reference
(E0 = 0.00 V, DE = 125 mV) [31,32]. Electrolyte solutions
were prepared from freshly distilled dichloromethane or
tetrahydrofuran solutions and [nBu4N]PF6 (dried in oil-
pump vacuum at 120 ꢁC, c = 0.1 M). The organometallic
complexes were added at c = 1 mM. Cyclic voltammo-
grams were recorded at a scan rate of 100 mV sꢀ1 using a
Radiometer Copenhagen DEA 101 Digital Electrochemical
analyzer with an IMT 102 Electrochemical Interface. Ele-
mental analyses were performed with a Vario EL, Elemen-
tar Analysensysteme GmbH (Hanau). Melting points were
determined using sealed nitrogen purged capillaries on a
Gallenkamp MFB 595 010 M melting point apparatus.
3. Experimental
3.1. General methods
All reactions were carried out under an atmosphere of
purified nitrogen using standard Schlenk techniques. n-
Hexane and tetrahydrofuran were purified by distillation
from sodium/benzophenone ketyl; dichloromethane was
purified by distillation from phosphorus pentoxide. Trieth-
ylamine was dried by distillation from KOH. Infrared spec-
tra were recorded with a Perkin–Elmer FT-IR 1000
spectrometer. NMR spectra were recorded with a Bruker
1
Avance 250 spectrometer. H NMR spectra were recorded
at 250.130 MHz (internal standard, relative to CDCl3, d
7.26) and 13C{1H}NMR spectra at 62.902 MHz (internal
standard, relative to CDCl3, d 77.16). Chemical shifts are
reported in d units (parts per million) downfield from tetra-
methylsilane with the solvent as the reference signal.
31P{1H}NMR spectra were recorded at 101.254 MHz with
P(OMe3) as external standard (d 139 ppm, relative to 85%
3.2. General remarks
I–C6H4–C6H4–SC(O)Me (1) [33] Me3Si–C„CH (2) [34]
FcC„CH (6) [35] (g5-C5H5)(g5-C5H4PPh2)Fe (11) [36]

1540
K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
Table 6
Crystal and intensity collection data for 3, 7 and 10
3
7
10
Formula
Formula weight
Crystal color
C19H20OSiS
324.50
Colorless
0.4 · 0.3 · 0.1
Triclinic
C26H20FeOS
436.33
Orange
0.3 · 0.2 · 0.2
Orthorhombic
Pbca
C34H26AuOPS
710.54
Colorless
0.4 · 0.2 · 0.2
Triclinic
Crystal dimensions (mm)
Crystal system
Space group
ꢀ
ꢀ
P1
P1
˚
a (A)
10.2299(16)
16.263(3)
17.485(3)
72.296(2)
79.084(2)
85.944(2)
2720.9(7)
6
12.7684(9)
11.3473(8)
27.789(2)
–
–
–
4026.3(5)
8
1.440
1808
0.868
10.7472(8)
12.3863(9)
21.9950(11)
89.994(5)
93.363(5)
101.255(6)
2866.5(3)
4
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
qcalc (g cmꢀ3
F(000)
)
1.188
1032
0.244
1.646
1392
5.286
Absorption coefficient (mmꢀ1
)
Scan range H (ꢁ)
1.31–26.46
ꢀ12 6 h 6 12,
ꢀ19 6 k 6 20,
0 6 l 6 21
298(2)
30792
11132
11106
1.47–26.41
0 6 h 6 29,
0 6 k 6 14,
0 6 l 6 34
183(2)
46440
4643
4129
2.91–26.06
ꢀ13 6 h 6 13,
ꢀ15 6 k 6 15,
ꢀ27 6 l 6 27
100(2)
28510
11250
11250
Index ranges
Temperature (K)
Total reflections
Unique reflections
Data
Restraints
0
0
0
Parameter
607
263
680
R1, wR2 [I P 2r(I)]a,b
R1, wR2 (all data)a,b
Rint, Goodness-of-fit on F2 c
0.0609, 0.1759
0.0798, 0.1852
0.0315, 1.097
0.637, ꢀ0.342
0.0321, 0.0691
0.0545, 0.0790
0.0706, 1.027
0.280, ꢀ0.314
0.0234, 0.0515
0.0376, 0.0537
0.0238, 0.977
1.566, ꢀ1.491
ꢀ3
˚
Maximum and minimum peak in final Fourier map (e A
)
h
i
1=2
P
P
P
P
P
2
a
b
c
R1 ¼ ðjF o ꢀ jF cjjÞ= jF oj; wR2 ¼
ðwðF 2o ꢀ F 2c Þ Þ= ðwF o4Þ
.
2
W ¼ 1=½r2ðF 2oÞ þ ð0:0612PÞ ꢂ, P ¼ ðF o2 þ 2F 2cÞ=3.
h
i
2
1=2
S ¼
wðF 2o ꢀ F 2c Þ =ðn ꢀ pÞ
.
and (tht)AuCl (12) [37] were prepared following published
procedures. All other chemicals are commercially available
and were used as received.
660 (s), 622 (s), 564 (m), 537 (s), 502 (m). 1H NMR
(CDCl3): d 0.27 (s, 9H, SiMe3), 2.45 (s, 3H, CH3), 7.47
4
3
5
((AB)2-system, JHH = 2.3 Hz, JHH = 8.1 Hz, JHH
=
0.3 Hz, 2 H, oH/C6H4-SC(O)Me), 7.53 ((AB)2-system,
4. Synthesis of 3
4JHH = 2.0 Hz, 3JHH = 8.9 Hz, 5JHH = 0.5 Hz, 4H,
4
3
C„C–C6H4), 7.61 ((AB)2-system, JHH = 1.7 Hz, JHH
8.1 Hz, 2H,
=
Compound I–C6H4–C6H4–SAc (1) (1.00 g, 2.82 mmol)
was dissolved in 5 mL of tetrahydrofuran and Me3SiC„
CH (2) (0.41 g, 4.17 mmol), NEt(iC3H7)2 (0.65 g,
4.54 mmol), (PPh3)2PdCl2 (99.3 mg, 0.14 mmol, 5 mol%)
and [CuI] (26.9 mg, 0.14 mmol, 5 mol%) were added. After
36 h of stirring at 25 ꢁC all volatiles were removed in oil-
pump vacuum and the residue was purified by column
chromatography (column size: 20 · 3 cm, Silica gel, n-hex-
ane:dichloromethane = 1:1). Evaporation of the solvents in
oil-pump vacuum gave a colorless solid. Yield: 0.67 g
(2.08 mmol, 74% based on 1).
5JHH = 0.3 Hz, mH/C6H4-SC(O)Me).
13C{1H}NMR (CDCl3): d 0.1 (SiMe3); 30.4 (CH3), 95.5
(C„C–C6H4), 104.9 (C„C–C6H4), 122.7 (C„C–iC/
C6H4), 127.0 (C„C–C6H4), 127.4 (C–S), 127.9 (mC/
C6H4–SC(O)Me), 132.6 (C„C–C6H4), 134.9 (oC/C6H4–
SC(O)Me), 140.2 (C„C–pC/C6H4), 141.6 (pC/C6H4-
SC(O)Me), 194.1 (C@O). 29Si{1H} NMR (CDCl3): d
ꢀ17.63. ESI-MS [m/z (rel int)]: 325.11 [(M+H)+] (100).
5. Synthesis of 4
Elemental analysis: Anal. Calc. for C19H20OSSi
(324.10): C, 70.32; H, 6.21. Found: C, 70.22; H, 6.21%.
M.p: 100 ꢁC. IR (KBr): m [cmꢀ1] 3393 (m), 3030 (w), 2958
(s), 2153 (s) (mC„C), 1914 (w), 1707 (vs) (mC@O), 1509 (w),
1478 (s), 1388 (s), 1352 (s), 1250 (vs), 1191 (w), 1120 (vs),
1090 (vs), 1001 (s), 952 (s), 846 (vs), 814 (vs), 758 (vs),
Thioacetate 3 (80 mg, 0.24 mmol) was dissolved in 2 mL
of tetrahydrofuran at 25 ꢁC and 25% NH4OH(aq) (83.7 mg,
2.46 mmol) was added in one portion. After 20 min of stir-
ring at this temperature the reaction mixture was acidified
with 3 M HCl and was then extracted three times with
15 mL of dichloromethane. After evaporation of the

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1541
Table 7
Crystal and intensity collection data for 13–15
13
14
15
Formula
Formula weight
Crystal color
C22H19AuClFeP
603.62
Yellow
C38H30AuFeOPS
818.47
Yellow
C22H19AuFeIP
694.06
Yellow
Crystal dimensions (mm)
Crystal system
Space group
0.3 · 0.2 · 0.2
Monoclinic
P2(1)/c
8.3428(8)
18.8982(17)
12.9700(12)
94.594(2)
2038.3(3)
4
0.3 · 0.2 · 0.2
Monoclinic
P2(1)/c
9.1179(6)
24.2458(16)
15.1348(10)
102.7040(10)
3264.0(4)
4
0.4 · 0.25 · 0.15
Monoclinic
P2(1)/n
10.6915(8)
15.2519(11)
12.3902(9)
100.801(6)
1984.6(3)
4
˚
a (A)
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
Z
qcalc (g cmꢀ3
F(000)
)
1.967
1156
8.113
1.666
1608
5.076
2.323
1296
9.754
Absorption coefficient (mmꢀ1
)
Scan range H (ꢁ)
Index ranges
1.91–26.42
ꢀ10 6 h 6 10,
0 6 k 6 23,
0 6 l 6 16
293(2)
15457
4312
4166
1.61–26.41
ꢀ11 6 h 6 11,
0 6 k 6 30,
0 6 l 6 18
298(2)
37670
6878
6702
3.09–26.05
ꢀ13 6 h 6 13,
ꢀ18 6 k 6 18,
ꢀ12 6 l 6 15
100(2)
11348
3877
3877
Temperature (K)
Total reflections
Unique reflections
Data
Restraints
40
282
0
Parameter
211
457
235
R1, wR2 [I P 2r(I)]a,b
R1, wR2 (all data)a,b
Rint, Goodness-of-fit on F2 c
0.0457, 0.1021
0.0814, 0.1165
0.0755, 1.012
1.726, ꢀ1.476
0.0410, 0.0909
0.0722, 0.1027
0.0521, 1.082
1.300, ꢀ1.066
0.0199, 0.0468
0.0237, 0.0478
0.0266, 1.059
1.326, ꢀ1.647
ꢀ3
˚
Maximum and minimum peak in final Fourier map (e A
)
h
i
1=2
P
P
P
P
P
2
a
b
c
R1 ¼ ðjF o ꢀ jF cjjÞ= jF oj; wR2 ¼
ðwðF 2o ꢀ F 2c Þ Þ= ðwF o4Þ
.
2
W ¼ 1=½r2ðF 2oÞ þ ð0:0612PÞ ꢂ, P ¼ ðF o2 þ 2F 2c Þ=3.
h
i
2
1=2
S ¼
wðF 2o ꢀ F 2c Þ =ðn ꢀ pÞ
.
100
300
250
200
150
80
60
40
20
0
8
4
I
I
3
100
50
0
5
-50
-20
-0.5
0.0
0.5
1.0
1.5
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00
EFeC / mV
EFeC / mV
Fig. 10. Cyclic voltammogram of 3 and 5 in dichloromethane at 25 ꢁC,
Fig. 11. Cyclic voltammogram of 4 and 8 in dichloromethane at 25 ꢁC,
[nBu4N]PF6 supporting electrolyte (0.1 M), scan rate = 100 mV sꢀ4
positive going scan.
,
[nBu4N]PF6 supporting electrolyte (0.1 M), scan rate = 100 mV sꢀ4
positive going scan.
,
solvent of the combined organic fractions in oil-pump vac-
uum a colorless solid was obtained. Yield: 66.0 mg
(0.23 mmol, 95% based on 3).
Elemental analysis: Anal. Calc. for C17H18SSi (282.48):
C, 72.28; H, 6.42. Found: C, 71.28; H, 6.63%. mp:
134 ꢁC. IR (KBr): m[cmꢀ1] 3447 (w), 3078 (w), 3028 (w),

1542
K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
2955 (m) (mCH3), 2896 (w), 2567 (w) (mSꢀH), 2156 (s) (mC„C),
1654 (w), 1593 (m), 1484 (s), 1396 (m), 1253 (s), 1244 (s),
1134 (w), 1103 (m), 1002 (w), 867 (vs), 843 (vs), 811 (vs),
759 (s), 698 (w), 658 (m), 553 (w), 512 (m). 1H NMR
(CDCl3): d 0.26 (s, 9H, SiMe3), 3.49 (s, 1 H, SH), 7.33
was purified by column chromatography (column size:
25 · 2 cm, Silica gel, n-hexane:dichloromethane = 3:2).
Evaporation of the solvents in oil-pump vacuum gave a
orange-brown solid. Yield: 1.03 g (2.35 mmol, 83% based
on 1).
4
3
5
((AB)2-system, JHH = 2.2 Hz, JHH = 8.1 Hz, JHH
=
=
Elemental analysis: Anal. Calc. for C26H20FeOS
(436.09): C, 71.57; H, 4.62. Found: C, 70.97; H, 4.72%.
M.p: 147 ꢁC. IR (KBr): m [cmꢀ1] 3099 (w) (mAryl–H), 2962
(m), 2200 (m) (mC„C), 1698 (vs) (mC@O), 1653 (m) (mC@C),
1484 (m), 1413 (m), 1387 (m), 1354 (m), 1261 (s), 1106
(s), 1033 (s), 961 (m), 923 (m), 857 (m), 814 (vs) (dAryl–H),
612 (s), 564 (m), 538 (m), 504 (s), 473 (m). 1H NMR
4
0.4 Hz, 2H, oH/C6H4-SH), 7.45 ((AB)2-system, JHH
3
5
2.0 Hz, JHH = 8.1 Hz, JHH = 0.4 Hz, 2 H, mH/C6H4-
4
3
SH), 7.49, 7.51 ((AB)2-system, JHH = 1.9 Hz, JHH
=
5
4
8.1 Hz, JHH = 0.5 Hz, JHH = 1.8 Hz, 4H, C„C–C6H4).
13C{1H}NMR (CDCl3): d 0.1 (SiMe3), 126.6 (C„C–
C6H4), 127.7 (mC/C6H4-SH), 129.9 (C„C–C6H4), 132.6
(oC/C6H4-SH).29Si{1H} NMR (CDCl3): d ꢀ17.69. ESI-
MS [m/z (rel int)]: 282.9 [M+] (5).
3
(CDCl3): d 2.46 (s, 3H, CH3), 4.28 (pt, JHH = 1.8 Hz,
2H, bH/C5H4), 4.28 (s, 5H, C5H5), 4.55 (pt, 3JHH = 1.8 Hz,
2H, aH/C5H4), 7.50 ((AB)2-system, 4JHH = 2.1 Hz,
5
6. Synthesis of 5
3JHH = 8.1 Hz, JHH = 0.4 Hz, 2H, oH/C6H4-SC(O)Me),
7.58 ((AB)2-system, 4JHH = 0.1 Hz, 3JHH = 8.9 Hz,
4
To 3 (0.34 g, 1.04 mmol) dissolved in 20 mL of tetra-
hydrofuran, acetic acid (0.27 g, 4.50 mmol) and acetic
anhydride (0.42 g, 4.09 mmol) was added. Afterward tet-
rabutylammonium fluoride hydrate (0.67 g, 2.58 mmol)
dissolved in 30 mL tetrahydrofuran was dropwise added.
After stirring over night at 25 ꢁC the solvents were
removed in oil-pump vacuum and the residue was puri-
fied by column chromatography (column size: 20 ·
3 cm, Silica gel, n-hexane:dichloromethane = 1:2). The
solvents were removed from the eluate in oil-pump vac-
uum to leave a colorless solid. Yield: 0.26 g (1.01 mmol,
97% based on 3).
5JHH = 0.4 Hz, JHH = 3.7 Hz, 4H, C„C–C6H4), 7.65
4
3
5
((AB)2-system, JHH = 2.0 Hz, JHH = 8.1 Hz, JHH
=
0.4 Hz, 2 H, mH/C6H4–SC(O)Me).13C{1H}NMR (CDCl3):
d 30.3 (CH3), 65.2 (iC/C5H4), 69.0 (bC/C5H4), 70.1 (C5H5),
71.5 (aC/C5H4), 85.6 (C„C–C6H4), 89.7 (C„C–C6H4),
123.6 (C„C–iC/C6H4), 127.1 (C„C–C6H4), 127.2 (C–S),
127.7 (mC/C6H4-SC(O)Me), 131.9 (C„C–C6H4), 134.9
(oC/C6H4-SC(O)Me), 139.2 (C„C–pC/C6H4), 141.6 (pC/
C6H4-SC(O)Me), 194.0 (C@O). ESI-MS [m/z (rel. int.)]:
436.09 [M+] (10).
8. Synthesis of 8
Elemental analysis: Anal. Calc. for C16H12OS (252.06):
C, 76.16; H, 4.79. Found: C, 75.88; H, 4.90%. M.p:
113 ꢁC. IR (KBr): m [cmꢀ1] 3272 (s) (m„C–H), 3025 (w),
2922 (w), 2103 (w) (mC„C), 1915 (w), 1693 (vs) (mC@O),
1481 (s), 1387 (m), 1352 (m), 1255 (w), 1125 (s),1112 (s),
1097 (m), 1003 (m), 943 (m), 854 (m), 818 (vs), 676 (m),
660 (m), 627 (s), 579 (w), 560 (w), 537 (m), 517 (w), 449
(w). 1H NMR (CDCl3): d 2.45 (s, 3 H, CH3), 3.15 (s,
The same procedure as used in the synthesis of 4 was
applied in the preparation of 8. Fc–C„C–C6H4–C6H4–
SAc (7) (100.0 mg, 0.23 mmol) and 25% NH4OH(aq)
(78.0 mg, 2.29 mmol) were reacted. After appropriate
work-up, complex 8 was obtained as a orange-brown solid.
Yield: 85.9 mg (0.21 mmol, 95% based on 7).
Elemental analysis: Anal. Calc. for C24H18FeS (394.05):
C, 73.10; H, 4.60. Found: C, 72.80; H, 4.75%. M.p: 158 ꢁC.
IR (KBr): m [cmꢀ1] 3080 (w) (mArylꢀH), 2959 (w), 2922 (w),
2848 (w), 2553 (w) (mSꢀH), 2369 (w), 2199 (w) (mC„C), 1654
(m) (mC@C), 1557 (w), 1488 (m), 1395 (w), 1260 (m), 1103
(m), 1023 (m), 919 (w), 812 (vs) (dAryl–H), 500 (m).1H
4
3
1H, HC„C), 7.48 ((AB)2-system, JHH = 1.9 Hz, JHH
=
5
8.1 Hz, JHH = 0.4 Hz, 2H, oH/C6H4–SC(O)Me), 7.55,
7.57 ((AB)2-system, 4JHH = 2.0 Hz, 3JHH = 8.0 Hz,
2
5JHH = 0.6 Hz, JHH = 1.8 Hz, 4H, C„C–C6H4), 7.62
4
3
5
((AB)2-system, JHH = 2.1 Hz, JHH = 8.1 Hz, JHH
=
0.4 Hz, 2H, mH/C6H4-SC(O)Me). 13C{1H}NMR (CDCl3):
d 30.4 (CH3), 78.3 (C„C–C6H4), 83.5 (C„C–C6H4),
121.7 (C„C–iC/C6H4), 127.2 (C„C–C6H4), 127.5 (C–S),
127.9 (mC/C6H4–SC(O)Me), 132.8 (C„C–C6H4), 135.0
(oC/C6H4-SC(O)Me), 140.6 (C„C–pC/C6H4), 141.5 (pC/
C6H4-SC(O)Me), 194.0 (C@O).
NMR (CDCl3): d 3.59 (s, 1H, SH), 4.17 (pt, JHH = 1.7
3
Hz, 2H, bH/C5H4), 4.17 (s, 5H, C5H5), 4.44 (pt,
3JHH = 1.7 Hz, 2H, aH/C5H4), 7.35 ((AB)2-system,
3
5
4JHH = 2.1 Hz, JHH = 8.1 Hz, JHH = 0.4 Hz, 2H, oH/
4
3
C6H4–SH), 7.48 ((AB)2-system, JHH = 2.2 Hz, JHH
=
8.1 Hz, JHH = 0.4 Hz, 2H, mH/C6H4-SH), 7.51, 7.54
5
4
3
5
((AB)2-system, JHH = 1.7 Hz, JHH = 8.0 Hz, JHH
=
4
7. Synthesis of 7
0.5 Hz, JHH = 2.2 Hz, 4H, C„C–C6H4).13C{1H}NMR
(CDCl3): d 65.3 (iC/C5H4), 69.0 (bC/C5H4), 70.1 (C5H5),
71.5 (aC/C5H4), 85.7 (C„C–C6H4), 89.4 (C„C–C6H4),
123.1 (C„C–iC/C6H4), 126.7 (C„C–C6H4), 127.6 (mC/
C6H4–SH), 129.9 (oC/C6H4–SH), 130.4 (iC/C6H4–SH),
131.9 (C„C–C6H4), 138.0 (pC/C6H4–SH), 139.5
(C„C–pC/C6H4). ESI-MS [m/z (rel int)]: 394.03 [M+]
(100).
To FcC„CH (6) (0.72 g, 3.41 mmol) and I–C6H4–
C6H4–SAc (1) (1.00 g, 2.84 mmol) in 80 mL of triethyl-
amine, (PPh3)2PdCl2 (99.8 mg, 0.14 mmol, 5 mol%) and
[CuI] (54.2 mg, 0.28 mmol, 10 mol%) were added at
25 ꢁC. After 24 h of stirring at 50 ꢁC all volatiles were
removed in oil-pump vacuum and the title compound

K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
1543
9. Synthesis of 10
the solvents were removed in oil-pump vacuum and the res-
idue was purified by column chromatography (column size:
25 · 2 cm, Silica gel, n-hexane:tetrahydrofuran = 7:1).
Evaporation of the solvents in oil-pump vacuum gave a
yellow solid. Yield: 140.0 mg (0.17 mmol, 53% based on
13) of 14 and 6.87 mg (0.009 mmol, 3% based on 13) of 15.
14: Elemental analysis: Anal. Calc. for C38H30AuFeOPS
(818.08): C, 55.76; H, 3.69. Found: C, 56.03; H, 4.01%. IR
(KBr): m [cmꢀ1] 3072 (m), 2956 (m), 2113 (w) (mC„C), 1909
(w), 1704 (vs) (mC@O), 1598 (m), 1544 (w), 1510 (w), 1479
(s), 1435 (s) (mP–Ph), 1387 (m), 1353 (m), 1307 (m), 1218
(m), 1172 (m), 1103 (vs), 1027 (m), 1001 (m), 950 (m),
816 (vs), 747 (m), 687 (s), 611 (m), 553 (m), 526 (m), 496
To (Ph3P)AuCl (9) (149.1 mg, 0.30 mmol) and HC„C–
C6H4–C6H4–SAc (5) (83.6 mg, 0.33 mmol) in 5 mL of tet-
rahydrofuran were added 10 mL of triethylamine. After
1 h of stirring at 25 ꢁC all volatiles were removed in oil-
pump vacuum and the residue was purified by column
chromatography (column size: 25 · 2 cm, Silica gel, n-hex-
ane:dichloromethane = 1:2). After evaporation of the sol-
vents in oil-pump vacuum, 10 could be isolated as a
colorless solid. Yield: 124.0 mg (0.17 mmol, 58% based
on 9).
Elemental analysis: Anal. Calc. for C34H26AuOPS
(710.11): C, 57.47; H, 3.69. Found: C, 58.23; H, 4.31%.
M.p: 151 ꢁC. IR (KBr): m [cmꢀ1] 3049 (m), 2922 (s), 2852
(m), 2106 (w) (mC„C), 1701 (vs) (mC@O), 1595 (w), 1478
(s), 1434 (s) (mP–Ph), 1387 (w), 1350 (w), 1261 (w), 1180
(w), 1099 (vs), 1025 (w), 1000 (w), 948 (w), 817 (vs), 746
(m), 692 (vs), 610 (m), 536 (vs). 1H NMR (CDCl3): d
2.43 (s, 3H, CH3), 7.41–7.63 (m, 23H, C6H4,C6H5).
13C{1H}NMR (CDCl3): d 30.4 (CH3), 124.7 (C„C–iC/
C6H4), 126.8 (C„C–C6H4), 127.8 (mC/C6H4-SC(O)Me),
1
(m), 471 (m), 449 (m). H NMR (CDCl3): d 2.43 (s, 3H,
CH3), 4.20 (s, 5H, C5H5), 4.39 (bs, 2H, aH/C5H4), 4.55
(bs, 2H, bH/C5H4), 7.38–7.65 (m, 18H, C6H4,
C6H5).13C{1H}NMR (CDCl3): d 30.4 (CH3), 68.0 (iC/
3
C5H4), 70.1 (C5H5), 72.4 (d, JCP = 9.6 Hz, C19), 73.6 (d,
2JCP = 13.9 Hz, aC/C5H4), 126.8 (C„C–C6H4), 127.7
3
(mC/C6H4–SC(O)Me), 128.9 (d, JCP = 11.5 Hz, mC/
2
o
C6H5), 132.9 (C„C–C6H4), 133.8 (d, JCP = 13.9 Hz, C/
C6H5),
134.8
(oC/C6H4-SC(O)Me).
31P{1H}NMR
3
129.3 (d, JCP = 11.0 Hz, mC/C6H5), 130.3 (C–S), 131.7
(CDCl3): d 36.40 (s). ESI-MS [m/z (rel int)]: 818.07 [M+]
(38).
4
(d, JCP = 2.4 Hz, pC/C6H5), 133.0 Hz (C„C–C6H4),
2
134.4 (d, JCP = 13.4 Hz, oC/C6H5), 134.9 (oC/C6H4–
15: Elemental analysis: Anal. Calc. for C22H19AuFeIP
(693.93): C, 38.07; H, 2.76. Found: C, 38.88; H, 2.72%.
M.p: 193 ꢁC. IR (KBr): m [cmꢀ1] 2920 (m), 1654 (m),
1480 (m), 1433 (vs), 1385 (m), 1309 (m), 1195 (m), 1175
(s), 1100 (vs), 1071 (m), 1027 (s), 999 (m), 908 (w), 825
(vs), 748 (vs), 695 (vs), 627 (m), 555 (vs), 521 (vs).1H
SC(O)Me), 138.4 (C„C–pC/C6H4), 142.0 (pC/C6H4-
SC(O)Me), 194.3 (C@O). 31P{1H}NMR (CDCl3): d 41.29
(s).
10. Synthesis of 13
a
NMR (CDCl3): d 4.21 (s, 5H, C5H5), 4.37 (bs, 2 H, H/
To 220 mg (0.686 mmol) of (tht)AuCl (2) dissolved in
10 mL of tetrahydrofuran were added 260 mg (0.703 mmol)
of FcPPh2 (1) dissolved in 20 mL of tetrahydrofuran during
1 h. After 1 h of stirring at 25 ꢁC all volatiles were removed
in oil-pump vacuum. The remaining orange solid was puri-
fied by column chromatography (column size: 25 · 2 cm,
Silica gel, diethyl ether). The product was obtained as a yel-
low solid. Yield: 295 mg (0.49 mmol, 71% based on 12).
Elemental analysis: Anal. Calc. for C22H19AuClFeP
(602.63): C, 43.85; H, 3.18. Found: C, 44.12; H, 3.20%.
M.p: 151 ꢁC.1H NMR (CDCl3): d 4.20 (s, 5H, C5H5),
4.36 (dt, 2H, C5H4), 4.57 (m, 2H, C5H4), 7.41–7.62 (m,
C5H4), 4.56 (bs, 2H, bH/C5H4), 7.39-7.65 (m, 10 H,
C6H5). 13C{1H}NMR (CDCl3): d 68.9 (iC/C5H4), 70.2
3
(C5H5), 72.5 (d, JCP = 9.1 Hz, bC/C5H4), 73.5 (d,
3
2JCP = 14.3 Hz, aC/C5H4), 128.9 (d, JCP = 11.5 Hz, mC/
1
C6H5), 131.5 (d, JCP = 59.5 Hz, iC/C6H5), 131.6 (d,
2
4JCP = 2.8 Hz, pC/C6H5), 133.5 (d, JCP = 13.9 Hz, oC/
C6H5). 31P{1H}NMR (CDCl3): d 34.65 (s). ESI-MS [m/z
(rel int)]: 694.00 [M+] (53).
12. X-ray structure determination
For data collection of 3, 7, 10 and 13–15 a Bruker
10H, C6H5). 13C{1H}NMR (CDCl3):
d
69.0 (d,
Smart 1K CCD diffractometer with graphite monochro-
1JCP = 75.1 Hz, iC/C5H4), 70.2 (C5H5), 72.6 (d,
matized Mo Ka radiation (k = 0.71073 A) was used. For
˚
3JCP = 8.9 Hz, bC/C5H4), 73.5 (d, JCP = 14.1 Hz, aC/
protection against oxygen and moisture, the preparation
of single crystals was preformed in perfluoro alkyl ether
(ABCR GmbH&Co KG; viscosity 1600 cSt). Data collec-
tion and cell determination has been done with the pro-
gram SMART [38,39]. For data integration and refinement
of the unit cell the program SAINT was used [39]. The
space group was determined using the program XPREP
[39] and the absorption has been corrected semi-empiri-
cally with SADABS [40]. The structures were solved by
direct methods with the program SHELXS-97 [41] and
refined by full-matrix least-squares procedures on F2,
using SHELXL-97 [42].
2
C5H4), 129.0 (d, JCP = 11.8 Hz, mC/C6H5), 131.0 (d,
3
i
4
1JCP = 62.2 Hz, C/C6H5), 131.7 (d, JCP = 1.9 Hz, pC/
2
o
C6H5), 133.6 (d, JCP = 13.7 Hz, C/C6H5). 31P{1H}NMR
(CDCl3): d 27.6 (s).
11. Synthesis of 14 and 15
FcPPh2-AuCl (13) (200 mg, 0.33 mmol) and HC„C–
C6H4-C6H4-SAc (5) (100 mg, 0.39 mmol) were dissolved
in 5 mL of tetrahydrofuran. Triethylamine (10 mL) and
[CuI] (2 mol%) were added. After 2 h of stirring at 25 ꢁC

1544
K. Ro¨ßler et al. / Journal of Organometallic Chemistry 692 (2007) 1530–1545
(h) J.F. Smalley, H.O. Finklea, C.E.D. Chidsey, M.R. Linford, S.E.
All non-hydrogen atoms were fully refined anisotropi-
Creager, J.P. Ferraris, K. Chalfant, T. Zawodzinsk, S.W. Feldberg,
M.D. Newton, J. Am. Chem. Soc. 125 (2003) 2004;
(i) D.M. Adams, L. Brus, C.E.D. Chidsey, S. Creager, C. Creutz,
C.R. Kagan, P.V. Kamat, M. Lieberman, S. Lindsay, R.A. Marcus,
R.M. Metzger, M.E. Michel-Beyerle, J.R. Miller, M.D. Newton,
D.R. Rolison, O. Sankey, K.S. Schanze, J. Yardley, X. Zhu, J. Phys.
Chem. B. 107 (2003) 6668;
cally in their local positions. The hydrogen atom positions
have been refined with a riding model.
13. Supplementary material
CCDC 624420, 624419, 624417, 624418, 624421 and
624416 contain the supplementary crystallographic data
for 3, 7, 10, 13, 14 and 15. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
(j) P. Lang, Z. Mekhalif, B. Rat, F. Garnier, J. Electroanal. Chem.
441 (1998) 83.
[14] (a) For example D. Taher, B. Walfort, G. van Koten, H. Lang,
Inorg. Chem. Commun. 9 (2006) 955;
(b) H. Lang, T. Stein, S. Back, G. Rheinwald, J. Organomet. Chem.
689 (2004) 2690;
(c) S. Ko¨cher, G.P.M. van Klink, G. van Koten, H. Lang, J.
Organomet. Chem. 691 (2006) 3319;
(d) H. Lang, R. Packheiser, B. Walfort, Organometallics 25 (2006)
1836;
(e) S. Back, W. Frosch, I. del Rio, G. van Koten, H. Lang, Inorg.
Chem. Commun. 2 (1999) 584;
Acknowledgement
Financial support from the Deutsche Forschungsgemein
schaft and the Fonds der chemischen is gratefully acknowl-
edged. We are grateful to Mario R. for many fruitful
discussions.
(f) For further species see: D.T. Gryko, F. Zhao, A.A. Yasseri, K.M.
Roth, D.F. Bocian, W.G. Kuhr, J.S. Lindsey, J. Org. Chem. 65
(2000) 7356;
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