Polymeric and macrocyclic gold(I) complexes with bridging dithiolate and diphosphine ligands

Article abstract of DOI:10.1016/j.ica.2006.01.018

The reaction of digold(I) diphosphine complexes [Au₂(O₂CCF₃)₂(μ-Ph₂P-X -PPh₂)] with dithiols HS-Y-SH can give either macrocyclic complexes [Au₂(μ-S-Y-S)(μ-Ph₂P-X-PPh₂)] or polymeric complexes [Au₂(μ-S-Y-S)(μ-Ph₂P-X-PPh₂)] _n. The structures of the macrocyclic complex [Au₂{μ-(S-4-C₆H₄)₂S}{μ -Ph₂P(CH₂)₄PPh₂}], and the polymeric complexes [Au_n{μ-(S-CH₂CO₂CH₂CH ₂O)₂-1,4-C₆H₄}_n(μ- trans-Ph₂PCH{double bond, long}CHPPh₂)_n] and [Au_n{μ-(S-CH₂CO₂CH₂CH ₂O)₂-1,5-C₁₀H₆}_n(μ -trans-Ph₂PCH{double bond, long}CHPPh₂)_n] have been determined. Evidence is presented that the complexes exist primarily as macrocycles in solution and that, in favorable cases, ring-opening polymerization occurs during crystallization.

Full text of DOI:10.1016/j.ica.2006.01.018

Inorganica Chimica Acta 359 (2006) 3605–3616
www.elsevier.com/locate/ica
Polymeric and macrocyclic gold(I) complexes with bridging
dithiolate and diphosphine ligands
*
William J. Hunks, Michael C. Jennings, Richard J. Puddephatt
Department of Chemistry, University of Western Ontario, London, Ont., Canada N6A 5B7
Received 31 October 2005; received in revised form 2 January 2006; accepted 2 January 2006
Available online 24 February 2006
Dedicated to Professor D.M.P. Mingos.
Abstract
The reaction of digold(I) diphosphine complexes [Au2(O2CCF3)2(l-Ph2P–X–PPh2)] with dithiols HS–Y–SH can give either macrocy-
clic complexes [Au2(l-S–Y–S)(l-Ph2P–X–PPh2)] or polymeric complexes [Au2(l-S–Y–S)(l-Ph2P–X–PPh2)]n. The structures of the
macrocyclic complex [Au2{l-(S-4-C6H4)2S}{l-Ph2P(CH2)4PPh2}], and the polymeric complexes [Aun{l-(S–CH2CO2CH2CH2O)2-1,4-
C6H4}n(l-trans-Ph2PCH@CHPPh2)n] and [Aun{l-(S–CH2CO2CH2CH2O)2-1,5-C10H6}n(l-trans-Ph2PCH@CHPPh2)n] have been deter-
mined. Evidence is presented that the complexes exist primarily as macrocycles in solution and that, in favorable cases, ring-opening
polymerization occurs during crystallization.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Gold; Dithiolate; Diphosphine; Macrocycle; Polymer; Ring-opening polymerization
1. Introduction
Several simple gold(I) complexes are polymeric in nature,
including the simple halogen or thiolate bridged gold(I)
complexes (A, Chart 1) [3]. Gold polymers involving diacet-
ylides with diphosphine or di-isonitrile ligands have also
been described, although the inherent skeletal rigidity of
these linear materials, and their correspondingly low solu-
bilities, hindered structural characterization [16,17]. Exam-
ples of structurally characterized gold(I) polymers are
limited. They can incorporate linear P–Au–P (B, Chart 1),
P–Au–N (C, Chart 1) or P–Au–O linkages, or tricoordinate
P2AuCl (D, Chart 1) or P3Au groups [16–23]. An important
example is the thiolate bridged antiarthritic drug gold(I) thi-
omalate, which contains linear S–Au–S groups (A, Chart 1)
[14].
The isolation of crystalline polymers can be accomplished
as a result of the lability of many gold(I)–ligand bonds, and it
is typical that solutions contain low molecular weight oligo-
mers or macrocycles which associate during crystallization
to form the polymers [16–23]. The interconversion between
macrocycles and polymers was first demonstrated in cationic
Metal containing polymers have been studied intensely
since the incorporation of metal centers into polymer
chains can lead to useful catalytic, electrical, optical, or
magnetic materials, which are not possible with the purely
organic analogs [1]. The thiolate derivatives are the most
useful of all gold complexes in present and potential indus-
trial applications, with uses in gold pastes, self-assembled
monolayers, chemical vapor deposition, luminescent
materials and pharmacology [2–4], and so there is intense
interest in the synthesis and properties of these compounds
[3–15]. In gold(I) complexes, intermolecular aurophilic
goldꢀ ꢀ ꢀgold bonding can be used in the formation of supra-
molecular architectures, for example in the cross-linking of
polymer chains or in the induction of chain folding [3–15].
*
Corresponding author. Tel.: +1 519 679 2111; fax: +1 519 679 6033.
E-mail addresses: pudd@uwo.ca, icarjp@uwo.ca (R.J. Puddephatt).
0020-1693/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.01.018

3606
W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
2. Results and discussion
Ph
Ph
X
X
P
n
2n+
Au Au
Au
Au
P
Ph
Ph
2.1. Synthesis of gold(I) dithiolate complexes
X
X
P
The new dithiol ligands were prepared by the alkylation
of aromatic diphenols with chloroethanol in base [31,32],
followed by condensation of the product alcohol with
mercaptoacetic acid [33]. For example, the reaction 2-chlo-
roethanol with 1,4-dihydroxybenzene gave 1,4-C6H4-
(OCH2CH2OH)2, which reacted with mercaptoacetic acid
to give the dithiol 1,4-C6H4(OCH2CH2O2CCH2SH)2 (1)
(Scheme 2). The dithiols R(OCH2CH2O2CCH2SH)2 with
R = 1,5-C10H6 (2), 4,40-C6H4C6H4 (3), 4,40-CMe2(C6H4)2
(4), were prepared similarly (Scheme 3). The more rigid
dithiol 4,40-S(C6H4SH)2 (5), the dithiol without a central
aromatic group (–CH2O2CCH2SH)2 (6), and the dithiol
with additional ether units 4,40-C6H4C6H4(OCH2CH2-
OCH2CH2OCH2CH2O2CCH2SH)2 (7), were prepared for
comparison (Schemes 4–6). The dithiols 1–7 were charac-
terized by their NMR and IR spectra and by MS.
The gold(I) diphosphine dithiolate complexes were read-
ily prepared by reaction of two equivalents of
[AuCl(SMe2)] with the corresponding diphosphine ligand,
PP, to give [Au2Cl2(l-P–X–P)], followed by reaction with
silver trifluoroacetate to give [Au2(O2CCF3)2(l-PP)], and
then by reaction of the gold(I) trifluoroacetate complex
with a dithiol ligand (HS–Y–SH), with displacement of
the weakly bonded trifluoroacetate ligands with loss of tri-
fluoroacetic acid [34], to give the product [Au2(l-S–Y–S)(l-
P–X–P)]. The syntheses are illustrated in Schemes 2–6.
These gold(I) dithiolate complexes were isolated as colour-
less air-stable solids, most of which were soluble in nitro-
benzene or dichloromethane, or in a mixture of these
solvents. For example, the dithiol 1 and diphosphine
ligands Ph2P(CH2)nPPh2 gave the macrocyclic complexes
8 [8a, n = 1; 8b, n = 2; 8c, n = 3; 8d, n = 4; 8e, n = 5; 8f,
n = 6] while the diphosphine ligand trans-Ph2PCH@
CHPPh2 gave a macrocycle 8g in solution but a polymer
8g* in the solid state (Scheme 2). The dithiols 2–7 gave sim-
ilar complexes 9–14, respectively.
X = Cl, Br, I, SR
A
Ph
Ph
Au
Ph
Ph
P
2n+
Ph
Ph
Au
Ph
P
P
Ph
Ph
P
Ph
Au
N
Au
Ph
P
Ph
B
Cl
Cl
Au
Fe
Cp2
Fe
Au
Cp2
P
P
P
P
Ph Ph
P
Ph Ph
N
Ph Ph
Ph Ph
Ph Ph
n
Au
C, X = (CH2)n
D
Chart 1. Some polymeric gold(I) complexes.
complexes of gold(I) with a combination of the bridging
ligands trans-1,4-bis(pyridyl)ethene gold(I) complexes with
diphosphines Ph2P(CH2)nPPh2. The structure changed from
a ring when n = 2, to a sinusoidal polymer when n = 3, to a
stretched linear polymer when n = 4, as the Auꢀ ꢀ ꢀAu separa-
tion increased (Scheme 1). The aim of the present work was
to find a system in which dithiolate ligands would be used in
place of trans-1,4-bis(pyridyl)ethane, and so give neutral
macrocycles or polymers, and to gain further insight into
ring-opening polymerization of coordination compounds.
Numerous eight-membered macrocyclic gold(I) com-
plexes have been prepared by using dithiocarbamate or
dithiophosphate ligands [3,24]. Larger rings (10–14 atoms)
have been prepared, for example by combining gold(I) with
1,3-propanedithiol and the diphosphines Ph2P(CH2)nPPh2
(n = 2–5) as shown in Scheme 1 [25–30]. Insoluble side prod-
ucts, thought to have polymeric structures, were obtained in
several cases and the similar reactions with 1,4-butanedithiol
gave only the insoluble, polymeric material [25]. We antici-
pated that incorporation of more flexible aliphatic and ester
groups in the backbone of the dithiol would increase the sol-
ubility of the gold(I) complexes, and that diphosphine
ligands which favor either the syn or anti conformation could
be used to influence the equilibrium between macrocyclic
and ring-opened isomeric forms of the products [16,17,20].
The synthesis and structural characterization of gold(I)
thiolate macrocycles of formula [R(OCH2CH2O2CCH2-
SAu)2- (l-Ph2P(CH2)nPPh2)] (n = 1–6), and the first exam-
ples of linear P–Au–S coordinated neutral gold-polymers
using the rigid diphosphine trans-1,2-bis(diphenylphosph-
ino)ethylene, are described below. A preliminary account
of a part of this work has been published [30].
The complexes 8 gave simple NMR spectra as expected
for a macrocyclic structure. For example, complex 8a gave
1
single resonances in the H NMR spectrum for the pheny-
lene group at d = 6.70 and for each methylene group at
d = 4.30 [CO2CH2], 3.95 [ArOCH2], and 3.75 [CH2S] and
a single resonance in the 31P NMR spectrum at d = 30.4.
The ESI-MS gave a peak at m/z = 1123 corresponding to
[8a+H]+ and no higher mass peaks. The complex with
the diphosphine ligand trans-Ph2PCH@CHPPh2 was
shown to have the polymeric structure 8g* in the solid state,
as described below, but it appears to have the macrocyclic
1
structure 8g in solution (Scheme 2). Thus, the H NMR
parameters for 8g are similar to those for 8a, and the 31P
NMR spectrum contained a single resonance, whereas a
polymer 8g* is expected to give broader, more complex
spectra. In support, the ESI-MS gave
a peak at
m/z = 1135 corresponding to [8g+H]+ and no higher mass

W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
3607
2n+
Au
X
Ph
P Ph
Ph
X
4+
P
Ph
Ph
Ph
Ph
Ph
Au
P
P
Au
Au
N
N
N
N
Au
N
N
X
Ph
Ph
Au
P
Au
P
P
P
Ph
Ph
Ph
Ph
Ph
Ph
Au
N
X
X = (CH2)n, n = 3-5
X = (CH2)n, n = 1, 2
X
Ph
Ph
N
P
P
Ph
Ph
Au
S
Ph Ph
P
Au
Au
S
S
S
X
(CH2)m
Au
P
P
Ph
Ph Ph
Ph
X = (CH2)n, n = 2 - 5
m = 3
X = (CH2)n, n = 2 - 5
Scheme 1. Equilibrium between macrocycles and ring-opened polymers.
peaks, and an accurate mass determination was in good
agreement with the expected value.
Complete NMR data for the gold thiolate complexes 9–
11 are listed in Section 4. Complex 10a was insoluble and
so is likely to have a polymeric structure in the solid state.
The gold(I) thiolates obtained from the ligands
S(C6H4SH)2 (Scheme 4) and (–CH2O2CCH2SH)2 (Scheme
5) were characterized similarly. However, the complexes
12g and 13g were insoluble, and so the equilibrium between
macrocycle and polymer is presumed to be displaced
towards the polymeric form when compared to the other
dithiolates studied. The polymeric complexes 12g and 13g
were thermally stable up to 280 °C, whereupon they gave
sharp decomposition to elemental gold.
Complexes containing chains of polyether units have
been widely used throughout supramolecular chemistry,
and are often used to bind alkali and alkaline earth metal
cations [35], or in the self-assembly of catenanes and
rotaxanes [36–38]. The organization of oligo(ethylene gly-
col) terminated alkanethiolates chemisorbed onto gold
In complex 9a, [1,5-C10H6(OCH2CH2O2CCH2SAu)2(l-
dppm)], Scheme 3, the CH2SAu group gives a singlet reso-
nances at d = 3.85 in the 1H NMR, shifted downfield from
the free ligand by 0.54 ppm. A single phosphorus resonance
was observed at d = 30.8, indicating formation of a macro-
cyclic complex. For complex 9g, [1,5-C10H6(OCH2CH2O2-
CCH2SAu)2(l-trans-Ph2PCH@CHPPh2)], the CH2SAu
protons gave a resonance at d = 3.53 in the 1H NMR,
and a single resonance in the 31P NMR at d = 35.0. The
freshly prepared complex 9g was freely soluble in the reac-
tion solution but, following crystallization, it was sparingly
soluble in dichloromethane or nitrobenzene. These data
suggest a macrocyclic structure 9g in solution but a poly-
meric structure 9g* of the solid complex, and this interpre-
tation is supported by ESI-MS data for the solution and by
X-ray structure determination of the crystalline complex.

3608
W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
O
O
O
O
Ph
P
Ph
X
SH
SH
X
O
O
SH
SH
O
S
S
Au
Au
Ph2P
Au
PPh2
Au
O
Y
O
O
O
Y
O
O
+
O
O
O
O
O
O
CF3
P
O
CF3
Ph
Ph
O
O
1
9a - 11g
2 - 4
- CF3CO2H
O
Ph
Ph
S
Au
P
O
O
O
Ph
P
Ph
Y
S
S
Au
Au
O
O
O
P
O
Au S
Ph
Ph
9g* - 11g*
3, 10; Y = 4,4'-(C6H4)2
X
O
2, 9; Y = 1,5-C10H6
O
O
P
Ph
Ph
O
8a-8f, X = (CH2)n, n = 1 - 6
8g, X = trans-CH=CH
O
Ph
Ph
S
Au
P
O
O
4, 11; Y = Me2C(4-C6H4)2
9a - 11a; X = CH2
9b - 11b; X = (CH2)2
9c - 11c; X = (CH2)3
9d - 11d; X = (CH2)4
9e - 11e; X = (CH2)5
9f - 11f; X = (CH2)6
Ph
P
Ph
P
P
Ph
Ph
O
O
Au S
Me
Me
Ph
Ph
x
O
9g - 11g; X = trans-CH=CH
8g*
Scheme 2. Dithiolate complexes obtained from the dithiol 1.
Scheme 3. The dithiolate complexes 9–11.
surfaces has shown to be aided by intermolecular interac-
tions among the chains [39]. In the present work, the dithiol
ligand [4,40-C6H4C6H4{(OCH2CH2)3OCOCH2SH}2] was
prepared and converted to the macrocyclic complexes
SH
S
Ph
P
Au
Au
1
Ph
14a–14g (Scheme 6). The H NMR spectra of these com-
plexes gave well-resolved resonances for the dithiol and
diphosphine protons, and the 31P NMR spectra each con-
tained a single resonance. The structures in solution are
therefore proposed to be the macrocycles.
The spectroscopic data for the complexes suggested for-
mation of gold(I) diphosphine dithiolate macrocycles in
each case in solution. However, the solution and solid state
structures might differ, and the structures of the complexes
8g, 9g, and 12d were determined crystallographically, in
order to provide a benchmark.
X
S
S
P
Ph
Ph
SH
S
5
X = (CH2)n; 12a - 12f, n = 1 - 6
Ph
Ph
S
P
S
Au
P
Ph
Au
S
12g
x
Ph
2.2. Structures of the complexes
Scheme 4. The dithiolate complexes 12.
The molecular structure of the 19-atom ring complex
12d is shown in Fig. 1. The ring structure is slightly twisted,
with a dihedral angle P(1)–Au(1)–Au(2)–P(2) = 29.5°,
resulting from the displacement of the S–Au groups on
opposite sides of the S(2)–S(1)–S(3) plane [C(61)–S(3)–
Au(1) = 103.3(2)°]. The bond lengths Au(1)–S(3) =
2.303(1), Au(1)–P(1) = 2.262(1), and C(61)–S(3) =
1.77(1) A are typical for linear phosphine gold-thiolate
complexes [3–10,40–44], and the gold atoms have approxi-
mately linear stereochemistry, with P(1)–Au(1)–S(3) =
176.2(1)°. The hinge angle C(54)–S(1)–C(64) = 102.2°, with
˚

W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
3609
O
O
Ph
Ph
O
S
S
Au
Au
P
O
SH
SH
X
P
O
O
Ph
Ph
O
O
6
X = (CH2)n; 13a-f, n = 1 - 6
O
O
Ph
Ph
Au
S
S
Au
P
O
O
P
Ph
13g
Ph
x
˚
Fig. 1. A view of the structure of complex 12d. Selected bond lengths (A)
Scheme 5. The dithiolate complexes 13.
and angles (°): Au(1)–P(1), 2.262(1); Au(1)–S(3), 2.303(1); Au(2)–P(2),
2.263(1); Au(2)–S(2), 2.298(1); S(3)–C(61), 1.770(5); S(2)–C(51), 1.775(5);
S(1)–C(54), 1.761(5); S(1)–C(64), 1.779(5); P(1)–Au(1)–S(3), 176.21(5);
P(2)–Au(2)–S(2), 176.02(5); C(61)–S(3)–Au(1), 103.3(2); C(51)–S(2)–
Au(2), 103.0(2); C(54)–S(1)–C(64), 102.2(2).
O
O
SH
O
O
O
coordinated to a phosphine and thiolate ligand with angle
P–Au–S = 178.1(1)°, and the pitch of the polymer is
˚
20.99 A. There is an inversion center in the middle of
the hydroquinone ring, resulting in equivalency of the
thioglycol chains on either side. The diphosphine has the
symmetry-imposed anti conformation, with dihedral angle
Au–P(1)–P(1A)–Au(A) = 180°. The plane of the hydroqui-
none ring is oriented orthogonal to the Pꢀ ꢀ ꢀP axis, result-
ing in a spiraling chain structure. The association between
neighboring polymer chains occurs through p-stacking
between phenyl groups and through weak intermolecular
O
O
O
O
SH
S
O
O
7
O
O
Au
P
O
O
˚
˚
Auꢀ ꢀ ꢀS (3.70 A) and Sꢀ ꢀ ꢀS (3.60 A) interactions. The
˚
diphosphine Pꢀ ꢀ ꢀP bite distances of 4.49 A is too long to
X
O
O
O
Au
P
S
O
O
X = (CH2)n; 14a - 14f, n = 1 - 6
X = trans-CH=CH, 14g
Scheme 6. The polyether dithiolate complexes 14.
aryl rings twisted by 37.1° and 128.1° about the plane
defined by the sulfur bridge and the two ipso carbon atoms.
These angles are similar to those in the acetylide complex
[S(4-C6H4OCH2CCAu)2(Ph2P(CH2)4PPh2)], which has
the hinge angle C–S–C = 104.3(3)° and aryl twist angles
of 1.1° and 97.2° [45]. The closest intramolecular approach
˚
of gold atoms in complex 12d is 8.33 A, giving a slightly
wider ring than in the diacetylide derivatives. The shortest
˚
intermolecular Auꢀ ꢀ ꢀAu distance is 6.05 A, indicating that
Fig. 2. Views of the structure of complex 8g*: (a) part of a single polymer
no aurophilic interactions are present in the solid state
structure of complex 12d.
Complexes 8g* and 9g* have similar polymeric struc-
tures. In complex 8g*, Fig. 2, each gold atom is linearly
chain and (b) the association with neighboring chains. Selected bond
˚
lengths (A) and angles (°): Au–P(1), 2.256(2); Au–S(21), 2.296(3); S(21)–
C(22), 1.80(1); C(23)–O(24), 1.17(1); C(23)–O(25), 1.39(2); P(1)–Au–S(21),
178.1(1); C(22)–S(21)–Au, 103.6(4); O(24)–C(23)–O(25), 122(1).

3610
W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
be obtained. The novel coordination polymers 8g* and 9g*
(Figs. 2 and 3) were prepared using the diphosphine
ligand trans-bis(diphenylphosphino)ethylene, in combina-
tion with dithiols [Ar(OCH2CH2O2CCH2SH)2], with
Ar = C6H4 or C10H6. The ligand trans-Ph2PCH@CHPPh2
has a natural tendency to adopt the anti conformation of
the two PPh2 units, and this favors the polymer over the
macrocycle, even in combination with the highly flexible
dithiolate ligands used in this work. These polymeric
complexes have high thermal stability, and decompose
only on heating to about 280 °C, leaving a residue of
metallic gold.
4. Experimental
The reagents 1,5-C10H6(OCH2CH2OH)2, 1,4-C6H4(OCH2-
CH2OH)2, 4,40-C6H4C6H4(OCH2CH2OH)2, CMe2(C6H4-
OCH2CH2OH)2 and 4,40-C6H4C6H4{(OCH2CH2)3OH}2
were prepared according to the literature methods
[31,32,46]. Subsequent preparation of the new dithiolate
ligands followed the known general procedure [33]. The
gold(I) diphosphine complexes were prepared following
standard protocols [13,20].
Fig. 3. Views of the structure of complex 9g*, showing a single polymer
chain and the association between polymer chains. Selected bond distances
and angles: Au(1)–P(1), 2.257(3); Au(1)–S(1), 2.300(3); S(1)–C(1), 1.80(1);
O(2)–C(2), 1.34(2); C(3)–C(4), 1.45(2); O(2)–C(3), 1.47(1); O(3)–C(5),
1.37(1); C(2)–O(1), 1.22(1); O(3)–C(4), 1.47(2); P(1)–Au(1)–S(1), 178.9(1),
C(1)–S(1)–Au(1), 104.4(5).
NMR spectra were recorded using a Varian Mercury
1
allow aurophilic interactions between the coordinated gold
400 MHz spectrometer. H and 13C NMR chemical shifts
are reported relative to TMS, while 31P chemical shifts
are reported relative to an 85% H3PO4 external standard.
All reactions involving gold reagents were performed in
darkened flasks.
˚
atoms (intrachain Auꢀ ꢀ ꢀAu = 4.95 A). Alternating chains
align in a criss-cross pattern in the lattice (Fig. 2b).
Complex 9g* forms a similar stretched one-dimensional
˚
polymer, with a pitch of 21.74 A, as shown in Fig. 3. The
chains connecting the thiolate donor to the naphthalene
bridge are helical, with each pair having opposite helicity.
The packing of the polymers is similar to 8g*, with individ-
ual chains linked through Auꢀ ꢀ ꢀS, Sꢀ ꢀ ꢀS, and p–p intermo-
lecular interactions, with interchain distances Auꢀ ꢀ ꢀS =
[1,5-C10H6(OCH2CH2O2CCH2SH)2] (2). 1,5-C10H6-
(OCH2CH2OH)2 (2.50 g, 10.07 mmol) and TsOH
(0.639 g, 3.37 mmol) were dissolved in toluene (100 mL).
Excess MgSO4 (ꢁ2 g) and mercaptoacetic acid (2.10 mL,
30.21 mmol) were added and the dark brown mixture
refluxed for 4 h. The mixture was filtered, and the filtrate
was washed sequentially with saturated aqueous NaHCO3
and H2O. The organic fraction was dried with MgSO4, fil-
tered, and the solvent removed. The residue was washed
with ether and collected by filtration. Yield: 2.50 g, 63%.
mp 97–98 °C. NMR in CDCl3: d(1H) = 7.87, 6.84 [d, 2H,
˚
˚
3.53 A and Sꢀ ꢀ ꢀS = 3.61 A. The interchain goldꢀ ꢀ ꢀgold dis-
˚
tance of 4.72 A is much too long to represent an aurophilic
interaction.
3. Conclusions
3
The dithiolate bridged gold macrocycles of composition
3J(HH) = 8 Hz, o,p-ArH], 7.39 [t, 2H, J(HH) = 8 Hz, m-
3
[Ar(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)nPPh2)]
and
ArH], 4.64 [t, 4H, J(HH) = 5 Hz, CH2CO2], 4.35 [t, 4H,
[(–CH2O2CCH2SAu)2(l-Ph2P(CH2)nPPh2)] with n = 1–6
have been prepared. The ring sizes range from 15-mem-
bered in 13a to 44-membered in 14f. The structure of one
example in the solid state, 12d, has been determined but
the less rigid complexes incorporating ester and ether
groups did not crystallize well. Nevertheless, they can be
assigned macrocyclic structures in solution based on the
NMR data and, in some cases, support from ESI-MS data.
It is not certain if the macrocyclic structures are maintained
in the solid state.
Polymeric gold(I) thiolate complexes are often insuffi-
ciently soluble to allow crystallization, but the presence
of the flexible ether and ester units in the organic back-
bone has proved to be useful in allowing crystalline poly-
mers of gold(I) with diphosphine and dithiolate ligands to
3J(HH) = 5 Hz, ArOCH2], 3.31 [d, 4H, 3J(HH) = 8 Hz,
CH2S], 2.02 [t, 2H, 3J(HH) = 8 Hz, SH]; d(13C) 171.19
(C@O), 154.18 (ipso C–O), 126.90 (ipso C–C), 125.49 (m-
ArH), 115.14, 106.04 (o,p-ArH), 66.34 (ArOCH2), 64.13
(CH2CO2), 26.71 (CH2SH). Anal. Calc. for C18H20O6S2:
C, 54.53; H, 5.08. Found: C, 55.01; H, 5.18%. EI-MS,
m/z = 396.070; calcd for C18H20O6S2: 396.070.
Similarly prepared were the following: [1,4-C6H4(OCH2-
CH2O2CCH2SH)2] (1). Yield: 88%. mp 78–79 °C. NMR in
CDCl3: d(1H) = 6.84 [s, 4H, ArH], 4.45 [t, 4H,
3J(HH) = 4 Hz, CH2CO2], 4.13 [t, 4H, 3J(HH) = 4 Hz,
ArOCH2], 3.29 [d, 4H, 3J(HH) = 8 Hz, CH2S], 2.01 [t,
3
2H, J(HH) = 8 Hz, SH]; d(13C) = 171.13 (C@O), 153.16
(ipso C), 115.94 (ArH), 66.63 (ArOCH2), 64.27 (CH2CO2),
26.67 (CH2SH). Anal. Calc. for C14H18O6S2: C, 48.54; H,

W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
3611
5.24. Found: C, 49.05; H, 5.52%. EI-MS, m/z = 346.054;
calcd for C14H18O6S2: 346.054. [4,40-C6H4C6H4(OCH2-
CH2O2CCH2SH)2] (3). Yield: 75%. mp 102–103 °C.
4H, CH2P], 1.88 [m, 2H, CH2]; d(31P) = 29.78 (s). Anal.
Calc. for C41H42Au2O6P2S2: C, 42.79; H, 3.68. Found: C,
42.19; H, 3.39%. [1,4-C6H4(OCH2CH2O2CCH2SAu)2(l-
Ph2P(CH2)4PPh2)] (8d). Yield: 73%. NMR in CD2Cl2:
d(1H) = 7.40–7.61 [m, 20H, Ph], 6.59 [s, 4H, ArH], 4.32
[t, 4H, J(HH) = 5 Hz, CH2CO2], 3.96 [t, 4H, J(HH) =
5 Hz, ArOCH2], 3.64 [s, 4H, CH2S], 2.41 [m, 4H, CH2P],
1.77 [m, 4H, CH2]. d(31P) = 33.44 (s). Anal. Calc. for
C42H44Au2O6P2S2: C, 43.31; H, 3.81. Found: C, 42.89;
H, 3.47%.
3
NMR in CDCl3: d(1H) = 7.41 [d, J(HH) = 9 Hz, 4H, m-
Ar], 6.90 [d, 3J(HH) = 9 Hz, 4H, o-Ar], 4.45 [t,
3
3
3
3J(HH) = 5 Hz, 4H, CH2O], 4.16 [t, J(HH) = 5 Hz, 4H,
ArOCH2], 3.25 [d, 3J(HH) = 8 Hz, CH2S], 1.96 [t,
3J(HH) = 8 Hz, 2H, SH]; d(13C) 171.16 (C@O), 157.76
(ipso C–O), 134.11 (ipso C–C), 128.06 (m-Ar) 115.12 (o-
Ar), 66.02 (ArOCH2), 64.22 (CH2O), 26.68 (CH2SH). Anal.
Calc. for C20H22O6S2: C, 56.85; H, 5.25. Found: C, 56.43;
H, 5.05%. EI-MS, m/z = 422.085; calcd for C20H22O6S2:
422.085. [CMe2{4-C6H4(OCH2CH2O2CCH2SH)}2] (4).
Yield: 82%. NMR in CDCl3: d(1H) 7.14 [d, 3J(HH) = 9 Hz,
4H, m-Ar], 6.81 [d, 3J(HH) = 9 Hz, 4H, o-Ar], 4.48 [t,
[1,4-C6H4(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)5PPh2)]
(8e). Yield: 90%. NMR in CD2Cl2: d(1H) = 7.45–7.69 [m,
3
20H, Ph], 6.67 [s, 4H, ArH], 4.35 [t, 4H, J(HH) = 5 Hz,
3
CH2CO2], 4.04 [t, 4H, J(HH) = 5 Hz, ArOCH2], 3.62 [s,
4H, CH2S], 2.45 [m, 4H, CH2P], 1.83 [m, 2H, CH2], 1.59
[m, 4H, CH2]. d(31P) = 32.63 (s). Anal. Calc. for C43H46-
Au2O6P2S2: C, 43.81; H, 3.91. Found: C, 43.43; H,
3.59%. [1,4-C6H4(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)6
PPh2)] (8f). Yield: 69%. NMR in CD2Cl2: d(1H) = 7.43–
7.69 [m, 20H, Ph], 6.69 [s, 4H, ArH], 4.35 [t, 4H,
3J(HH) = 5 Hz, CH2CO2], 4.03 [t, 4H, 3J(HH) = 5 Hz,
ArOCH2], 3.68 [s, 4H, CH2S], 2.42 [m, 4H, CH2P], 1.64
[m, 4H, CH2], 1.48 [m, 4H, CH2]. d(31P) = 34.90 (s). Anal.
Calc. for C40H38Au2O6P2S2: C, 44.30; H, 4.06. Found: C,
43.80; H, 3.70%. [1,4-C6H4(OCH2CH2O2CCH2SAu)2
(l-trans-Ph2PCH@CHPPh2)]n (8g). Yield: 95%. NMR in
CD2Cl2: d(1H) = 7.40–7.62 [m, 20H, Ph], 7.39 [t, 2H,
2J(HP) = 18 Hz, @CHP], 6.53 [s, 4H, ArH], 4.23 [t, 4H,
3J(HH) = 5 Hz, CH2CO2], 3.93 [t, 4H, 3J(HH) = 5 Hz,
ArOCH2], 3.58 [s, 4H, CH2S]. d(13C) = 173.54 (C@O),
152.71 (ipso C), 133.96, 132.42 (@CH, J(PC) = 155 Hz),
129.75 (CH2S), 116.41 (ArH), 66.97 (ArOCH2), 62.95
(CH2CO2). d(31P) = 35.68 (s). Anal. Calc. for C40H38Au2-
O6P2S2: C, 42.34; H, 3.38. Found: C, 41.71; H, 3.15%.
Crystals were grown by slow diffusion of petroleum ether
into a solution in CH2Cl2.
[1,5-C10H6(OCH2CH2O2CCH2SAu)2(l-Ph2PCH2PPh2)]
(9a). To a solution of [Au2Cl2(l-Ph2PCH2PPh2)] (0.250 g,
0.29 mmol) in CH2Cl2(10 mL), a solution of silver trifluo-
roacetate (0.136 g, 0.59 mmol) was added in MeOH
(2 mL). The reaction mixture was stirred for 30 min, then
filtered through celite to remove AgCl. Dithiol 2 (0.117 g,
0.29 mmol) in CH2Cl2 (2 mL) was added. The solution
was stirred for 3 h, then the product was precipitated by
addition of pentane (100 mL). The resulting colorless pow-
der was collected by filtration and washed with acetone and
ether. Yield: 0.272 g, 79%. NMR in CD2Cl2: d(1H) = 7.20–
7.45 [m, 20H, Ph], 7.68, 6.55 [m, 2H, ArH], 7.11 [m, 2H,
ArH], 4.49 [s, 4H, CH2CO2], 4.13 [s, 4H, ArOCH2], 3.85
[s, 4H, CH2S], 3.65 [m, 2H, CH2P]; d(31P) = 30.77 (s). Anal.
Calc. for C43H42Au2O6P2S2: C, 43.96; H, 3.60. Found: C,
43.26; H, 3.14%.
3
3J(HH) = 5 Hz, 4H, CH2O], 4.17 [t, J(HH) = 5 Hz, 4H,
ArOCH2], 3.29 [d, 3J(HH) = 8 Hz, CH2S], 2.01 [t,
3J(HH) = 8 Hz, 2H, SH], 1.63 [s, 6H, CMe2]. [4,40-
C6H4C6H4{(OCH2CH2)3OCOCH2SH}2] (7). Yield: 48%.
mp 79–80 °C. NMR in CDCl3: d(1H) = 7.46 [d,
3
3J(HH) = 8 Hz, 4H, m-Ar], 6.96 [d, J(HH) = 8 Hz, 4H,
o-Ar], 4.30 [t, 3J(HH) = 5 Hz, 4H, CH2O], 4.16 [t,
3
3J(HH) = 5 Hz, 4H, CH2O], 3.87 [t, J(HH) = 5 Hz, 4H,
CH2O], 3.74 [t, 3J(HH) = 5 Hz, 8H, CH2O], 3.70 [t,
3J(HH) = 5 Hz, 4H, ArOCH2], 3.28 [d, 3J(HH) = 8 Hz,
3
CH2S], 2.01 [t, J(HH) = 8 Hz, 2H, SH]; d(13C) = 171.16
(C@O), 158.08 (ipso C–O), 133.80 (ipso C–C), 127.92 (m-
Ar) 115.08 (o-Ar), 71.06 (ArOCH2), 70.90, 70.06, 69.20,
67.71, 64.97 (CH2O), 26.71 (CH2SH). EI-MS, m/z:
598.189; calcd for C20H22O6S2: 598.189.
[1,4-C6H4(OCH2CH2O2CCH2SAu)2(l-Ph2PCH2PPh2)]
(8a). To a solution of [Au2Cl2(l-Ph2PCH2PPh2)] (0.300 g,
0.35 mmol) in CH2Cl2 (10 mL), a solution of silver trifluo-
roacetate (0.161 g, 0.70 mmol) was added in MeOH
(2 mL). The reaction mixture was stirred for 30 min, then
filtered through celite to remove AgCl. Dithiol 1 (0.122 g,
0.35 mmol) in CH2Cl2 (2 mL) was added. The solution
was stirred for 3 h, then the product was precipitated by
addition of pentane (100 mL). The resulting colorless pow-
der was collected by filtration and washed with acetone and
ether. Yield: 0.234 g, 59%. NMR in CD2Cl2: d(1H) = 6.8–
7.3 [m, 20H, Ph], 6.70 [s, 4H, ArH], 4.30 [s, 4H, CH2CO2],
3.95 [s, 4H, ArOCH2], 3.75 [s, 4H, CH2S]; 3.65 [s, 2H,
CH2P]. d(31P) = 30.40 (s). Anal. Calc. for C39H38-
Au2O6P2S2: C, 41.72; H, 3.41. Found: C, 41.38; H, 3.41%.
Similarly, by use of the appropriate diphosphine ligand,
the following were prepared: [1,4-C6H4(OCH2CH2O2-
CCH2SAu)2(l-Ph2PCH2CH2PPh2)] (8b). Yield: 35%.
NMR in CD2Cl2: d(1H) = 7.40–7.70 [m, 20H, Ph], 6.50 [s,
4H, ArH], 4.35 [s, 4H, CH2CO2], 3.94 [s, 4H, ArOCH2],
3.53 [s, 4H, CH2S]; 2.74 [m, 4H, CH2P]. d(31P) = 34.55
(s). Anal. Calc. for C40H40Au2O6P2S2: C, 42.26; H, 3.55.
Found: C, 41.84; H, 3.23%. [1,4-C6H4(OCH2CH2O2CCH2-
SAu)2(l-Ph2P(CH2)3PPh2)] (8c). Yield: 84%. NMR in
CD2Cl2: d(1H) = 7.40–7.70 [m, 20H, Ph], 6.68 [s, 4H,
Similarly prepared, using the appropriate diphosphine
derivative, were the following: [1,5-C10H6(OCH2CH2-
O2CCH2SAu)2(l-Ph2P(CH2)2PPh2)] (9b). Yield: 57%.
NMR in CD2Cl2: d(1H) = 7.34–7.60 [m, 20H, Ph], 7.82,
6.54 [d, 2H, 3J(HH) = 8 Hz, ArH], 7.17 [t, 2H,
3
ArH], 4.31 [t, 4H, J(HH) = 4 Hz, CH2CO2], 4.01 [t, 4H,
3J(HH) = 4 Hz, ArOCH2], 3.54 [s, 4H, CH2S], 2.82 [m,

3612
W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
3J(HH) = 8 Hz, ArH], 4.41 [s, 4H, CH2CO2], 4.09 [s, 4H,
ArOCH2], 3.69 [s, 4H, CH2S], 2.61 [m, 4H, CH2P].
d(31P) = 35.46 (s). Anal. Calc. for C44H44Au2O6P2S2: C,
44.45; H, 3.73. Found: C, 43.90; H, 3.51%.
[1,5-C10H6(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)3PPh2)]
(9c). Yield: 83%. NMR in CD2Cl2: d(1H) = 7.38–7.59 [m,
der was collected by filtration and washed with acetone and
ether. Yield: 0.334 g, 82%. The compound was insoluble in
common organic solvents. Anal. Calc. for C45H42Au2O6-
P2S2: C, 45.08; H, 3.53. Found: C, 44.82; H, 3.28%.
Similarly, by use of the appropriate diphosphine ligand,
the following were prepared: [4,40-C6H4C6H4(OCH2-
CH2O2CCH2SAu)2(l-Ph2P(CH2)2PPh2)] (10b). Yield:
71%. NMR in nitrobenzene-d5: d(1H) = 7.63–7.80, 8.10
[m, 20H, Ph], 7.44 [m, 4H, Ar], 7.04 [m, 4H, Ar], 4.80 [s,
4H, CH2O], 4.53 [s, 4H, ArOCH2], 4.37 [s, 4H, CH2S],
3.41 [m, 4H, CH2P]. d(31P) = 31.19 (s). Anal. Calc. for
C46H44Au2O6P2S2: C, 45.55; H, 3.66. Found: C, 44.78;
H, 3.38%. [4,40-C6H4C6H4(OCH2CH2O2CCH2SAu)2(l-
Ph2P(CH2)3PPh2)] (10c). Yield: 84%. NMR in nitroben-
zene-d5: d(1H) = 7.61–7.64, 8.04 [m, 20H, Ph], 7.54 [d,
2J(HH) = 8 Hz, 4H, Ar], 7.06 [d, 3J(HH) = 8 Hz, 4H,
Ar], 4.76 [s, 4H, CH2O], 4.40 [s, 4H, ArOCH2], 4.15 [s,
4H, CH2S], 3.20 [m, 4H, CH2P], 2.23 [m, 2H, CH2].
d(31P) = 30.22 (s). Anal. Calc. for C47H46Au2O6P2S2: C,
46.01; H, 3.78. Found: C, 45.32; H, 3.67%. [4,40-
C6H4C6H4(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)4PPh2)]
(10d). Yield: 76%. NMR in nitrobenzene-d5: d(1H) = 7.61–
7.97 [m, 20H, Ph], 7.53 [d, 2J(HH) = 8 Hz, 4H, Ar], 7.04 [d,
3J(HH) = 8 Hz, 4H, Ar], 4.79 [s, 4H, CH2O], 4.43 [s, 4H,
ArOCH2], 4.15 [s, 4H, CH2S], 2.75 [m, 4H, CH2P], 2.12
[sbr, 4H, CH2]. d(31P) = 34.21 (s). Anal. Calc. for
C48H48Au2O6P2S2: C, 46.46; H, 3.90. Found: C, 45.89;
H, 3.62%. [4,40-C6H4C6H4(OCH2CH2O2CCH2SAu)2(l-
Ph2P(CH2)5PPh2)] (10e). Yield: 84%. NMR in CD2Cl2:
3
20H, Ph], 7.82, 6.39 [d, 2H, J(HH) = 8 Hz, ArH], 7.08
3
[t, 2H, J(HH) = 8 Hz, ArH], 4.49 [s, 4H, CH2CO2], 4.08
[s, 4H, ArOCH2], 3.56 [s, 4H, CH2S], 2.29 [m, 4H,
CH2P], 1.53 [m, 2H, CH2]. d(31P) = 31.27 (s). Anal. Calc.
for C45H46Au2O6P2S2: C, 44.93; H, 3.85. Found: C,
44.62, H, 3.77%. [1,5-C10H6(OCH2CH2O2CCH2SAu)2(l-
Ph2P(CH2)4PPh2)] (9d). Yield: 69%. NMR in CD2Cl2:
d(1H) = 7.39–7.59 [m, 20H, Ph], 7.79, 6.35 [d, 2H,
3
3J(HH) = 8 Hz, ArH], 7.11 [t, 2H, J(HH) = 8 Hz, ArH],
4.47 [s, 4H, CH2CO2], 4.06 [s, 4H, ArOCH2], 3.63 [s, 4H,
CH2S], 2.08 [m, 4H, CH2P], 1.47 [m, 4H, CH2].
d(31P) = 34.37 (s). Anal. Calc. for C46H48Au2O6P2S2: C,
45.40; H, 3.98. Found: C, 45.06, H, 3.84%.
[1,5-C10H6(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)5PPh2)]
(9e). Yield: 84%. NMR in CD2Cl2: d(1H) = 7.40–7.63 [m,
3
20H, Ph], 7.85, 6.55 [d, 2H, J(HH) = 8 Hz, ArH], 7.18
3
[t, 2H, J(HH) = 8 Hz, ArH], 4.48 [s, 4H, CH2CO2], 4.13
[s, 4H, ArOCH2], 3.57 [s, 4H, CH2S], 2.10 [m, 4H,
CH2P], 1.53 [m, 6H, CH2]. d(31P) = 34.63 (s). Anal. Calc.
for C47H50Au2O6P2S2: C, 45.86; H, 4.09. Found: C,
45.37; H, 3.87%. [1,5-C10H6(OCH2CH2O2CCH2SAu)2(l-
Ph2P(CH2)6PPh2)] (9f). Yield: 56%. NMR in CD2Cl2:
d(1H) 7.45–7.66 [m, 20H, Ph], 7.82, 6.39 [d, 2H,
3
3
3J(HH) = 8 Hz, ArH], 7.15 [t, 2H, J(HH) = 8 Hz, ArH],
d(1H) = 7.67–7.45 [m, 20H, Ph], 7.36 [d, J(HH) = 8 Hz,
4.49 [s, 4H, CH2CO2], 4.08 [s, 4H, ArOCH2], 3.61 [s, 4H,
CH2S]; 2.10 [m, 4H, CH2P], 1.5 [m, 8H, CH2].
d(31P) = 35.26 (s). Anal. Calc. for C48H52Au2O6P2S2: C,
46.31; H, 4.21. Found: C, 46.05; H, 3.97%. [1,5-C10H6-
(OCH2CH2O2CCH2SAu)2(l-trans-Ph2PCH@CHPPh2)]n
(9g). Yield: 88%. NMR in CDCl3: d(1H) = 7.30–7.50 [m,
4H, Ar], 6.83 [d, 3J(HH) = 8 Hz, 4H, Ar], 4.38 [s, 4H,
CH2O], 4.09 [s, 4H, ArOCH2], 3.62 [s, 4H, CH2S], 2.44
[m, 4H, CH2P], 1.76 [m, 2H, CH2], 1.60 [m, 4H, CH2].
d(31P) = 33.07 (s). Anal. Calc. for C49H50Au2O6P2S2: C,
46.90; H, 4.02. Found: C, 46.63; H, 3.79%. [4,40-
C6H4C6H4(OCH2CH2O2CCH2SAu)2(l-Ph2P(CH2)6PPh2)]
(10f). Yield: 58%. NMR in CD2Cl2: d(1H) = 7.68–7.45 [m,
20H, Ph], 7.35 [d, 3J(HH) = 8 Hz, 4H, Ar], 6.80 [d,
3J(HH) = 8 Hz, 4H, Ar], 4.39 [s, 4H, CH2O], 4.08 [s, 4H,
ArOCH2], 3.71 [s, 4H, CH2S], 2.38 [m, 4H, CH2P], 1.61
[m, 4H, CH2], 1.43 [m, 4H, CH2]; d(31P) = 35.02 (s). Anal.
Calc. for C50H52Au2O6P2S2: C, 47.33; H, 4.13. Found: C,
47.64; H, 3.72%. [4,40-C6H4C6H4(OCH2CH2O2CCH2-
SAu)2(l-trans-Ph2PCH@CHPPh2)]n (10g). Yield: 59%.
NMR in nitrobenzene-d5: d(1H) = 7.51–7.98 [m, 20H,
Ph], 7.49 [m, 4H, ArH], 7.08 [m, 6H, ArH and @CHP],
4.83 [s, 4H, CH2O], 4.42 [s, 4H, ArOCH2], 4.30 [s, 4H,
CH2S]; d(31P) = 30.55 (s). Anal. Calc. for C46H42-
Au2O6P2S2: C, 45.63; H, 3.50. Found: C, 45.10; H, 3.27%.
[CMe2{4-C6H4(OCH2CH2O2CCH2SAu)}2(l-Ph2PCH2-
PPh2)] (11a). To a solution of [Au2Cl2(l-Ph2PCH2PPh2)]
(0.200 g, 0.24 mmol) in CH2Cl2 (10 mL), a solution of sil-
ver trifluoroacetate (0.109 g, 0.47 mmol) was added in
MeOH (2 mL). The reaction mixture was stirred for
30 min, then filtered through celite to remove AgCl. Dithiol
4 (0.109 g, 0.24 mmol) in CH2Cl2 (2 mL) was added. The
solution was stirred for 3 h, then the product was precipi-
3
20H, Ph], 7.67, 6.45 [d, 2H, J(HH) = 8 Hz, ArH], 7.05
[t, 2H, 3J(HH) = 8 Hz, ArH], 7.10 [t, 2J(HP) = 19 Hz,
2H, @CHP], 4.32 [s, 4H, CH2CO2], 4.06 [s, 4H, ArOCH2],
3.53 [s, 4H, CH2S]. d(13C) = 171.20 (C@O), 154.07 (ipso C–
O), 133.95, 132.40 (@CHP, J(PC) = 156 Hz), 129.72
(CH2SAu), 126.83 (ipso C–C), 125.38 (m-ArH), 115.50,
106.40 (o,p-ArH), 66.71 (ArOCH2), 63.30 (CH2CO2).
d(31P) = 34.97 (s). Anal. Calc. for C44H42Au2O6P2-
S2 Æ CH2Cl2: C, 42.50; H, 3.49. Found: C, 42.01; H,
3.21%. Crystals of [C10H6(OCH2CH2O2CCH2SAu)2(l-
dppee)] Æ CH2Cl2 were grown by slow diffusion of ether into
a concentrated solution in CH2Cl2.
[4,40-C6H4C6H4(OCH2CH2O2CCH2SAu)2(l-Ph2PCH2-
PPh2)] (10a). To a solution of [Au2Cl2(l-Ph2PCH2PPh2)]
(0.300 g, 0.35 mmol) in CH2Cl2(10 mL), a solution of silver
trifluoroacetate (0.161 g, 0.70 mmol) was added in MeOH
(2 mL). The reaction mixture was stirred for 30 min, then
filtered through celite to remove AgCl. Dithiol 3 (0.134 g,
0.35 mmol) in CH2Cl2 (2 mL) was added. The solution
was stirred for 3 h, then the product was precipitated by
addition of pentane (100 mL). The resulting colorless pow-

W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
3613
tated by addition of pentane (100 mL). The resulting color-
less powder was collected by filtration and washed with
acetone and ether. Yield: 0.224 g, 77%. NMR in CD2Cl2:
d(1H) 7.61–7.56, 7.36–7.24 [m, 20H, Ph], 7.04 [d,
3J(HH) = 8 Hz, 4H, Ar], 6.70 [d, 3J(HH) = 8 Hz, 4H,
Ar], 4.35 [s, 4H, CH2O], 4.06 [s, 4H, ArOCH2], 3.74 [s,
4H, CH2S], 2.13 [m, 2H, CH2P], 1.58 [s, 6H, CMe2].
d(31P) = 30.97 (s). Anal. Calc. for C48H48Au2O6P2S2: C,
46.46; H, 3.90. Found: C, 45.96; H, 3.65%. [CMe2{4-
C6H4(OCH2CH2O2CCH2SAu)}2(l-Ph2P(CH2)2PPh2)] (11b).
Yield: 87%. NMR in CD2Cl2: d(1H) = 7.68–7.63, 7.46–
d(31P) = 35.51 (s). Anal. Calc. for C49H48O6P2S2Au2: C,
46.97; H, 3.86. Found: C, 46.20; H, 3.75%.
[S(4-C6H4SAu)2(l-Ph2PCH2PPh2)] (12a). To a solution
of [Au2Cl2(l-Ph2PCH2PPh2)] (0.250 g, 0.29 mmol) in
CH2Cl2(20 mL),
a solution of silver trifluoroacetate
(0.136 g, 0.59 mmol) was added in MeOH (2 mL). The
reaction mixture was stirred for 30 min, then filtered
through celite to remove AgCl. Dithiol 5 (0.074 g,
0.29 mmol) in CH2Cl2 (5 mL) was added. The solution
was stirred for 3 h, then the product was precipitated by
addition of pentane (100 mL). The resulting colorless pow-
der was collected by filtration and washed with acetone and
ether. Yield: 0.200 g, 66%. NMR in CD2Cl2: d(1H) = 7.05–
7.65 [m, 24H, Ph, Ar], 6.95 [m, 4H, Ar], 4.46 [m, 2H,
CH2P]. d(31P) = 36.62 (s). Anal. Calc. for C37H30Au2P2S3:
C, 43.28; H, 2.95. Found: C, 42.77; H, 2.64%.
Similarly, by use of the appropriate diphosphine ligand,
the following were prepared: [S(4-C6H4SAu)2(l-Ph2P(CH2)2-
PPh2)](12b). Yield: 58%. NMR inCD2Cl2: d(1H) = 7.30–7.50
[m, 24H, Ph, Ar], 6.90 [m, 4H, Ar], 2.80 [m, 4H, CH2P];
d(31P) = 35.90 (s). Anal. Calc. for C38H32Au2P2S3: C, 43.85;
H, 3.10. Found: C, 43.52; H, 2.84%. [S(4-C6H4SAu)2(l-
Ph2P(CH2)3PPh2)] (12c). Yield: 36%. NMR in CD2Cl2:
d(1H) = 7.31–7.58 [m, 24H, Ph, Ar], 6.92 [d, 4H,
3J(HH) = 8 Hz, Ar], 2.78 [m, 4H, CH2P], 1.08 [m, 2H,
CH2]; d(31P) = 32.22 (s). Anal. Calc. for C39H34Au2P2S3: C,
44.41; H, 3.25. Found: C, 43.50; H, 3.34%.
3
7.36 [m, 20H, Ph], 6.97 [d, J(HH) = 8 Hz, 4H, Ar], 6.65
3
[d, J(HH) = 8 Hz, 4H, Ar], 4.29 [s, 4H, CH2O], 4.03 [s,
4H, ArOCH2], 3.66 [s, 4H, CH2S], 2.79 [m, 4H, CH2P],
1.56 [s, 6H, CMe2]. d(31P) = 35.35 (s). Anal. Calc. for
C49H50Au2O6P2S2: C, 46.90; H, 4.02. Found: C, 46.64;
H, 3.99%.
[CMe2{4-C6H4(OCH2CH2O2CCH2SAu)}2(l-Ph2P-
(CH2)3PPh2)] (11c). Yield: 70%. NMR in CD2Cl2:
d(1H) = 7.68–7.63, 7.46–7.41 [m, 20H, Ph], 7.02 [d,
3J(HH) = 8 Hz, 4H, Ar], 6.66 [d, 3J(HH) = 8 Hz, 4H,
Ar], 4.32 [t, 3J(HH) = 4 Hz, 4H, CH2O], 4.03 [t,
3J(HH) = 4 Hz, 4H, ArOCH2], 3.50 [s, 4H, CH2S], 2.77
[m, 4H, CH2P], 1.83 [m, 2H, CH2], 1.58 [s, 6H, CMe2].
d(31P) = 30.39 (s). Anal. Calc. for C50H52Au2O6P2S2: C,
47.33; H, 4.13. Found: C, 47.37; H, 3.98%. [CMe2-
{4-C6H4(OCH2CH2O2CCH2SAu)}2(l-Ph2P(CH2)4PPh2)]
(11d). Yield: 74%. NMR in CD2Cl2: d(1H) = 7.63–7.58,
[S(4-C6H4SAu)2(l-Ph2P(CH2)4PPh2)] (12d). Yield: 47%.
3
7.47–7.38 [m, 20H, Ph], 6.99 [d, J(HH) = 9 Hz, 4H, m-
NMR in CD2Cl2: d(1H) = 7.36–7.59 [m, 24H, Ph, Ar], 6.93
Ar], 6.64 [d, 3J(HH) = 9 Hz, 4H, o-Ar], 4.33 [t,
[d, 4H, J(HH) = 8 Hz, Ar], 2.36 [m, 4H, CH2P], 1.71 [m,
3
3
3J(HH) = 5 Hz, 4H, CH2O], 4.03 [t, J(HH) = 5 Hz, 4H,
4H, CH2]; d(31P) = 35.29 (s). Anal. Calc. for
C40H36Au2P2S3: C,44.95; H,3.39. Found: C, 44.43; H,
3.30%. Crystals of [S(C6H4SAu)2(l-dppb)] Æ C6H5NO2
were grown from a solution of nitrobenzene and ether.
[S(4-C6H4SAu)2(l-Ph2P(CH2)5PPh2)] (12e). Yield: 45%.
NMR in CD2Cl2: d(1H) = 7.31–7.63 [m, 24H, Ph, Ar],
6.97 [d, 4H, 3J(HH) = 8 Hz, Ar], 2.40 [m, 4H, CH2P],
1.63 [m, 4H, CH2] 1.51 [m, 2H, CH2]; d(31P) = 33.44 (s).
Anal. Calc. for C41H38Au2P2S3: C, 45.48; H, 3.54. Found:
C, 44.93; H, 3.18%. [S(4-C6H4SAu)2(l-Ph2P(CH2)6PPh2)]
(12f). Yield: 53%. NMR in CD2Cl2: d(1H) = 7.40–7.66
ArOCH2], 3.57 [s, 4H, CH2S], 2.39 [m, 4H, CH2P], 1.73
[m, 4H, CH2], 1.58 [m, 2H, CH2], 1.58 [s, 6H, CMe2].
d(31P) = 34.38 (s). Anal. Calc. for C51H54O6P2S2Au2: C,
47.74; H, 4.24. Found: C, 47.22; H, 4.28%. [CMe2{4-
C6H4(OCH2CH2O2CCH2SAu)}2(l-Ph2P(CH2)5PPh2)] (11e).
Yield: 89%. NMR in CD2Cl2: d(1H) = 7.67–7.62, 7.49–
7.42 [m, 20H, Ph], 7.04 [d, 3J(HH) = 8 Hz, 4H, m-Ar],
3
6.68 [d, J(HH) = 8 Hz, 4H, o-Ar], 4.35 [s, 4H, CH2O],
4.06 [s, 4H, ArOCH2], 3.60 [s, 4H, CH2S], 2.45 [m, 4H,
CH2P], 1.80 [m, 2H, CH2], 1.57 [m, 4H, CH2], 1.60 [m,
6H, CMe2]. d(31P) = 32.87 (s). Anal. Calc. for
C52H56Au2O6P2S2: C, 48.15; H, 4.35. Found: C, 48.34;
H, 4.31%. [CMe2{4-C6H4(OCH2CH2O2CCH2SAu)}2(l-
Ph2P(CH2)6PPh2)] (11f). Yield: 75%. NMR in CD2Cl2:
d(1H) = 7.68–7.63, 7.50–7.39 [m, 20H, Ph], 7.04 [d,
3
[m, 24H, Ph, Ar], 6.99 [d, 4H, J(HH) = 8 Hz, Ar], 2.39
[m, 4H, CH2P], 1.59 [m, 4H, CH2], 1.37 [sbr, 4H, CH2];
d(31P) = 36.01 (s). Anal. Calc. for C42H40Au2P2S3: C,
45.99; H, 3.68. Found: C, 45.37; H, 3.70%. [S(4-
C6H4SAu)2(l-trans-Ph2PCH@CHPPh2)] (12g). Yield:
76%. Anal. Calc. for C38H30Au2P2S3: C, 43.94; H, 2.91.
Found: C, 43.45; H, 2.69%.
[(–CH2OCOCH2SAu)2(l-Ph2PCH2PPh2)] (13a). To a
solution of [Au2Cl2(l-Ph2PCH2PPh2)] (0.130 g, 0.15 mmol)
in thf (10 mL), a solution of silver trifluoroacetate (0.071 g,
0.31 mmol) was added in MeOH (2 mL). The reaction mix-
ture was stirred for 20 min, then filtered through celite to
remove AgCl. Dithiol 6 (27 lL, 0.15 mmol) was added.
The solution was stirred for 3 h, then the product was pre-
cipitated by addition of pentane (100 mL). The resulting
colorless powder was collected by filtration and washed
3
3J(HH) = 8 Hz, 4H, m-Ar], 6.69 [d, J(HH) = 8 Hz, 4H,
o-Ar], 4.36 [s, 4H, CH2O], 4.06 [s, 4H, ArOCH2], 3.62 [s,
4H, CH2S], 2.77 [m, 4H, CH2], 2.41 [m, 4H, CH2], 1.46
[sbr, 4H, CH2], 1.60 [s, 6H, CMe2]. d(31P) = 30.80 (s). Anal.
Calc. for C53H58O6P2S2Au2: C, 48.15; H, 4.35. Found:
C, 47.89; H, 4.31%. [CMe2{4-C6H4(OCH2CH2O2CCH2-
SAu)}2(l-trans-Ph2PCH@CHPPh2)]n (11g). Yield: 77%.
NMR in CD2Cl2: d(1H) = 7.57–7.37 [m, 22H, Ph and
@CHP], 6.96 [d, 3J(HH) = 8 Hz, 4H, m-Ar], 6.62 [d,
3J(HH) = 8 Hz, 4H, o-Ar], 4.26 [s, 4H, CH2O], 4.03 [s,
4H, ArOCH2], 3.55 [s, 4H, CH2S], 1.58 [s, 6H, CMe2].

3614
W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
with acetone and ether. Yield: 0.108 g, 71%. NMR in
CD2Cl2: d(1H) = 7.40–7.65 [m, 20H, Ph], 4.25 [s, 4H,
CH2O], 3.63 [s, 4H, CH2S], 3.95 [sbr, 2H, CH2P].
d(31P) = 30.42 (s). IR(Nujol): m(C„O) = 1728 cmꢂ1. Anal.
Calc. for C31H30Au2O4P2S2: C,37.74; H,3.06. Found: C,
37.88; H, 3.03%.
ArH], 4.28 [m, 4H, CH2O], 4.11 [m, 8H, CH2O], 3.80 [m,
4H, CH2O], 3.71 [m, 4H, CH2O], 3.62 [m, 4H, CH2O],
3.57 [s, 4H, CH2S], 3.09 [m, 4H, CH2P]. d(31P) = 33.50
(s). Anal. Calc. for C54H60O10P2S2Au2: C, 46.69; H, 4.35.
Found: C, 46.26; H, 4.15%. [4,40-C6H4- C6H4{(OCH2-
CH2)3OCOCH2SAu}2(l-Ph2P- (CH2)3PPh2)] (14c). Yield:
83%. NMR in CD2Cl2: d(1H) = 7.40–7.68 [m, 24H, Ph,
ArH], 6.91 [d, 4H, 3J(HH) = 8 Hz, ArH], 4.11 [m, 8H,
CH2O], 3.79 [t, 4H, 3J(HH) = 5 Hz, CH2O], 3.60 [m,
12H, CH2O] 3.52 [s, 4H, CH2S], 2.81 [m, 4H, CH2P],
1.86 [m, 2H, CH2]; d(31P) = 29.92 (s). Anal. Calc. for
C55H62O10P2S2Au2: C, 47.08; H, 4.45. Found: C, 47.39;
Similarly, by use of the appropriate diphosphine ligand,
the following were prepared: [(–CH2OCOCH2SAu)2(l-
Ph2P(CH2)2PPh2)] (13b). Yield: 77%. NMR in CD2Cl2:
d(1H) = 7.45–7.70 [m, 20H, Ph], 4.23 [s, 4H, CH2O], 3.55
[s, 4H, CH2S], 2.83 [m, 4H, CH2P]. d(31P) = 35.61 (s). Anal.
Calc. for C32H32Au2O4P2S2: C, 38.41; H, 3.22. Found: C,
38.68; H, 3.19%. [(–CH2OCOCH2SAu)2(l-Ph2P(CH2)3P-
Ph2)] (13c). Yield: 79%. NMR in CD2Cl2: d(1H) = 7.45–
7.70 [m, 20H, Ph], 4.15 [s, 4H, CH2O], 3.45 [s, 4H, CH2S],
2.80 [m, 4H, CH2P], 2.02 [m, 2H, CH2]; d(31P) = 32.19 (s).
Anal. Calc. for C33H34Au2O4P2S2: C, 39.06; H, 3.38.
Found: C, 38.77; H, 3.26%. [(–CH2OCOCH2SAu)2
(l-Ph2P(CH2)4PPh2)], [13d Æ (dppb)] (10d). Yield: 87%.
NMR in CD2Cl2: d(1H) = 7.45–7.70 [m, 20H, Ph], 4.24 [s,
4H, CH2O], 3.55 [s, 4H, CH2S], 2.51 [m, 4H, CH2P], 1.86
[m, 4H, CH2]; d(31P) = 34.68 (s). Anal. Calc. for
C34H36Au2O4P2S2: C, 39.70; H, 3.53. Found: C, 39.53; H,
3.42%. [(–CH2OCOCH2SAu)2(l-Ph2P(CH2)5PPh2)] (13e).
Yield: 0.208 g, 72%. NMR in CD2Cl2: d(1H) = 7.44–7.71
[m, 20H, Ph], 4.17 [s, 4H, CH2O], 3.51 [s, 4H, CH2S], 2.49
[m, 4H, CH2P], 1.72 [m, 6H, CH2]; d(31P) = 34.86 (s). Anal.
Calc. for C35H38Au2O4P2S2: C, 40.32; H, 3.67. Found: C,
39.76; H, 3.53%. [(–CH2OCOCH2SAu)2(l-Ph2P(CH2)6-
PPh2)] (13f). Yield: 85%. NMR in CD2Cl2: d(1H) = 7.45–
7.70 [m, 20H, Ph], 4.23 [s, 4H, CH2O], 3.52 [s, 4H, CH2S],
1.65 [m, 4H, CH2P], 1.54 [m, 8H, CH2]; d(31P) = 34.79 (s).
Anal. Calc. for C36H40Au2O4P2S2: C, 40.92; H, 3.82.
Found: C, 40.54; H, 3.92%. [(–CH2OCOCH2SAu)2(l-
trans-Ph2PCH@CHP- Ph2)] (13g). Yield: 0.323 g, 93%.
The compound is insoluble in all common organic solvents.
Anal. Calc. for C32H30Au2O4P2S2: C, 38.49; H, 3.03.
Found: C, 38.06; H, 2.86%.
H,
4.28%.
[4,40-C6H4C6H4{(OCH2CH2)3OCOCH2-
SAu}2(l-Ph2P- (CH2)4PPh2)] (14d). Yield: 77%. NMR in
CD2Cl2: d(1H) = 7.39–7.64 [m, 24H, Ph, ArH], 6.92 [d,
3
4H, J(HH) = 9.0 Hz, ArH], 4.12 [m, 8H, CH2O], 3.80 [t,
3
4H, J(HH) = 4.5 Hz, CH2O] 3.63 [m, 12H, CH2O], 3.60
[s, 4H, CH2S], 2.45 [m, 4H, CH2P], 1.80 [m, 4H, CH2];
d(31P) = 33.61 (s). Anal. Calc. for C56H64O10P2S2Au2: C,
47.46; H, 4.55. Found: C, 47.88; H, 4.41%. [4,40-
C6H4C6H4{(OCH2CH2)3OCOCH2SAu}2(l-Ph2P(CH2)5-
PPh2)] (14e). Yield: 75%. NMR in CD2Cl2: d(1H) = 7.42–
7.69 [m, 24H, Ph, ArH], 6.94 [s, 4H, 3J(HH) = 8 Hz,
ArH], 4.18 [t, 4H, 3J(HH) = 5 Hz, CH2O], 4.13 [t, 4H,
3J(HH) = 5 Hz, CH2O] 3.80 [t, 4H, 3J(HH) = 5 Hz,
CH2O] 3.64 [m, 12H, CH2O], 3.60 [s, 4H, CH2S], 2.46
[m, 4H, CH2P], 1.86 [m, 2H, CH2], 1.60 [m, 4H, CH2];
d(31P) = 32.70 (s). Anal. Calc. for C58H66O10P2S2Au2: C,
47.84; H, 4.65. Found: C, 47.83; H, 4.47%. [4,40-
C6H4C6H4{(OCH2CH2)3OCOCH2SAu}2(l-Ph2P(CH2)6-
PPh2)] (14f). Yield: 88%. NMR in CD2Cl2: d(1H) = 7.43–
3
7.68 [m, 24H, Ph, ArH], 6.93 [d, J(HH) = 8 Hz, ArH],
4.17 [t, 4H, 3J(HH) = 5 Hz, CH2O], 4.11 [t, 4H,
3J(HH) = 5 Hz, CH2O] 3.79 [t, 4H, 3J(HH) = 5 Hz,
CH2O] 3.63 [m, 12H, CH2O], 3.58 [s, 4H, CH2S], 2.44
[m, 4H, CH2P], 1.66 [m, 4H, CH2], 1.50 [m, 4H, CH2];
d(31P) 34.82 (s). Anal. Calc. for C59H68O10P2S2Au2: C,
48.20; H, 4.74. Found: C, 48.14; H, 4.05%. [4,40-C6H4-
C6H4{(OCH2CH2)3OCOCH2SAu}2(l-trans-Ph2PCH@CH-
PPh2)] (14g). Yield: 80%. NMR in CD2Cl2: d(1H) 7.40–7.63
[m, 24H, Ph, ArH], 6.93 [s, 4H, 3J(HH) = 9 Hz, ArH], 6.96
[4,40-C6H4C6H4{(OCH2CH2)3OCOCH2SAu}2(l-Ph2P-
CH2PPh2)] (14a). To a solution of [Au2Cl2(l-Ph2PCH2-
PPh2)] (0.250 g, 0.29 mmol) in CH2Cl2(10 mL), a solution
of silver trifluoroacetate (0.136 g, 0.59 mmol) was added
in MeOH (2 mL). The reaction mixture was stirred for
30 min, then filtered through celite to remove AgCl. Dithiol
7 (27 lL, 0.15 mmol) was added. The solution was stirred
for 3 h., then the product was precipitated by addition of
pentane (100 mL). The resulting colorless powder was col-
lected by filtration and washed with ether. Yield: 0.230 g,
57%. NMR in CD2Cl2: d(1H) = 7.21–7.47 [m, 24H, Ph,
2
[t, 2H, J(PH) = 18 Hz, @CHP] 4.12 [m, 4H, CH2O], 4.07
[m, 4H, CH2O] 3.80 [m, 4H, CH2O] 3.58 [m, 16H, CH2O,
CH2S]; d(31P) = 35.06 (s). Anal. Calc. for C54H58O10P2-
S2Au2: C, 46.76; H, 4.21. Found: C, 47.05; H, 4.01%.
5. X-ray structure determinations
Single crystals were mounted on glass fibers. Data were
collected using a Nonius Kappa CCD diffractometer, using
the program COLLECT for data collection, DENZO for cell
refinement and data reduction, SCALEPACK for the absorp-
tion correction, SHELXTL-NT 6.1 for structure solution by
direct methods and least squares refinement [47]. Crystal
and experimental details are given in Table 1.
3
ArH], 6.92 [d, 4H, J(HH) = 7 Hz, ArH], 4.20 [sbr, 4H,
CH2O], 4.10 [sbr, 4H, CH2O] 3.80 [sbr, 8H, CH2O] 3.64
[sbr, 8H, CH2O] 3.62 [s, 4H, CH2S], 3.60 [m, 2H, CH2P];
d(31P) = 30.49 (s). Anal. Calc. for C53H58- O10P2S2Au2:
C, 46.30; H, 4.25. Found: C, 45.96; H, 4.03%. [4,40-
C6H4C6H4{(OCH2CH2)3OCOCH2SAu}2(l-Ph2P(CH2)2-
PPh2)] (14b). Yield: 68%. NMR in CD2Cl2: d(1H) = 7.40–
7.64 [m, 24H, Ph, ArH], 6.93 [d, 4H, 3J(HH) = 8 Hz,
For complex 12d, all non-hydrogen atoms, including
those of the nitrobenzene solvate molecule, were refined

W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
3615
Table 1
Crystal data and experimental details
Complex
12d Æ PhNO2
8g* Æ 2C2H4Cl2
9g* Æ CH2Cl2
Formula
C46H41Au2NO2P2S3
1191.85
297(2)
C44H38Au2Cl4O6P2S2
1324.24
294(2)
C45H42Au2Cl2O6P2S2
1269.68
200(2)
Formula weight
T (K)
˚
k (A)
0.71073
0.71073
0.71073
Crystal system
Space group
Unit cell dimensions
triclinic
monoclinic
P2/n
monoclinic
P2/n
ꢀ
P1
˚
a (A)
12.2798(3)
13.5635(4)
14.0911(4)
105.296(1)
98.423(2)
99.449(2)
2188.24(10)
2
14.8337(8)
8.3956(4)
19.2351(10)
90
98.642(3)
90
2368.3(2)
2
1.857
16.0701(12)
8.5562(3)
19.9827(14)
90
105.700(2)
90
2645.1(3)
2
1.594
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
Z
Dcalc (Mg/m3)
Absorption coefficient (mmꢂ1
F(000)
1.809
6.951
1152
)
6.614
1276
5.820
1228
Number of reflections
26731
25101
10575
Number of independent reflections
Absorption correction
Data/restraints/parameters
Goodness-of-fit on F2
R1 [I > 2r(I)]
10012
4662
5880
integration
10012/0/505
0.930
0.0366
0.0790
integration
4662/30/301
0.967
0.0548
0.1285
integration
5880/0/267
0.947
0.0635
0.1666
wR2 [I > 2r(I)]
[4] Z.J. Guo, P.J. Sadler, Adv. Inorg. Chem. 49 (2000) 183.
[5] R. Balasubramanian, R. Guo, A.J. Mills, R.W. Murray, J. Am.
Chem. Soc. 127 (2005) 8126.
[6] Y. Negishi, K. Nobusada, T. Tsukuda, J. Am. Chem. Soc. 127 (2005)
5261.
[7] J.H. Chen, A.A. Mohamed, H.E. Abdou, J.A.K. Bauer, J.P. Fackler,
A.E. Bruce, M.R.M. Bruce, Chem. Commun. (2005) 1575.
[8] R.Y.C. Shin, G.K. Tan, L.L. Koh, J.J. Vittal, L.Y. Goh, Organo-
metallics 24 (2005) 539.
[9] C.K. Li, X.X. Lu, K.M.C. Wong, C.L. Chan, N.Y. Zhu, V.W.W.
Yam, Inorg. Chem. 43 (2004) 7421.
with anisotropic thermal parameters. The hydrogen atoms
were calculated geometrically and were riding on their
respective carbon atoms.
In complex 9g*, the centroid of the C10H6 ring, the cen-
ter of the trans-ethylene bond, and the carbon atom of the
dichloromethane solvate molecule sit on symmetry ele-
ments. All of the non-hydrogen atoms were refined with
anisotropic thermal parameters. Hydrogen atoms were
placed in the calculated geometrical positions. The complex
8g* was similar. The two dichloroethane solvate molecules
were treated with fixed C–Cl and C–C distances.
[10] B.C. Tzeng, J.H. Liao, G.H. Lee, S.M. Peng, Inorg. Chim. Acta 357
(2004) 1405.
[11] K. Nunokawa, K. Okazaki, S. Onaka, M. Ito, T. Sunahara, T.
Ozeki, H. Imai, K. Inoue, J. Organomet. Chem. 690 (2005) 1332.
[12] J.D.E.T. Wilton-Ely, A. Schier, N.W. Mitzel, H. Schmidbaur, J.
Chem. Soc., Dalton Trans. (2001) 1058.
Acknowledgements
We thank the NSERC (Canada) for financial support
and for a scholarship to W.H. R.J.P. thanks the Govern-
ment of Canada for a Canada Research Chair.
[13] M.J. Irwin, J.J. Vittal, G.P.A. Yap, R.J. Puddephatt, J. Am. Chem.
Soc. 118 (1996) 13101.
[14] R.J. Bau, J. Am. Chem. Soc. 120 (1998) 9380.
[15] A. Houlton, D.M.P. Mingos, D.M. Murphy, D.J. Williams, L.T.
Phang, J. Chem. Soc., Dalton Trans. (1993) 3629.
[16] R.J. Puddephatt, Chem. Commun. (1998) 1055.
[17] R.J. Puddephatt, Coord. Chem. Rev. 216 (2001) 313.
[18] M.C. Brandys, R.J. Puddephatt, J. Am. Chem. Soc. 123 (2001)
4839.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.ica.2006. 01.018.
[19] M.R. Wiseman, P.A. Marsh, P.T. Bishop, B.J. Brisdon, M.F.
Mahon, J. Am. Chem. Soc. 122 (2000) 12598.
References
[20] M.C. Brandys, R.J. Puddephatt, Chem. Commun. (2001) 1280.
[21] Z. Qin, M.C. Jennings, R.J. Puddephatt, Chem. Eur. J. 8 (2002)
735.
[22] T.J. Burchell, D.J. Eisler, M.C. Jennings, R.J. Puddephatt, Chem.
Commun. (2003) 2228.
[23] F. Mohr, M.C. Jennings, R.J. Puddephatt, Angew. Chem., Int. Ed.
Engl. 43 (2004) 969.
[24] J.P. Fackler Jr., Inorg. Chem. 41 (2002) 6959.
[1] I. Manners, Synthetic Metal-Containing Polymers, Wiley–VCH,
Weinheim, 2004.
[2] V.W.W. Yam, C.L. Chan, C.K. Li, K.M.C. Wong, Coord. Chem.
Rev. 216 (2001) 173.
[3] H. Schmidbaur, Gold: Progress in Chemistry, Biochemistry and
Technology, Wiley, New York, 1999.

3616
W.J. Hunks et al. / Inorganica Chimica Acta 359 (2006) 3605–3616
[25] R. Narayanaswamy, M.A. Young, E. Parkhurst, M. Ouellette, M.E.
Kerr, D.M. Ho, R.C. Elder, A.E. Bruce, M.R.M. Bruce, Inorg.
Chem. 32 (1993) 2506.
Prodi, H.G. Ricketts, J.F. Stoddart, M.S. Tolley, M. Venturi, A.J.P.
White, D.J. Williams, Chem. Eur. J. 3 (1997) 152.
[37] J.G. Hansen, N. Feeder, D.G. Hamilton, M.J. Gunter, J. Becher,
J.K.M. Sanders, Org. Lett. 2 (2000) 449.
´
[26] R.M. Davila, A. Elduque, T. Grant, R.J. Staples, J.P. Fackler Jr.,
Inorg. Chem. 32 (1993) 1749.
[38] E. Lindner, M.F. Gunther, H.A. Mayer, R. Fawzi, M. Steimann,
¨
[27] J.T.E. Wilton-Ely, A. Schier, N.W. Mitzel, H. Schmidbaur, Inorg.
Chem. 40 (2001) 1749.
Chem. Ber. 130 (1997) 1815.
[39] R. Valiokas, S. Svedhem, M. Ostblom, C.T. Svensson, B. Liedberg,
¨
[28] W.B. Jones, J. Yuan, R. Narayanaswamy, M.A. Young, R.C. Elder,
A.E. Bruce, M.R.M. Bruce, Inorg. Chem. 34 (1995) 1749.
J. Phys. Chem. B 105 (2001) 5459.
[40] L.S. Ahmed, W. Clegg, D.A. Davies, J.R. Dilworth, M.R.J.
Elsegood, D.V. Griffiths, L. Horsburgh, J.R. Miller, N. Wheatley,
Polyhedron 18 (1999) 593.
´
[29] R. Terroba, E.J. Fernandez, M.B. Hursthouse, M. Laguna, Polyhe-
dron 17 (1998) 2433.
[30] W.J. Hunks, M.C. Jennings, R.J. Puddephatt, Chem. Commun.
(2002) 1834.
[41] M. Nakamoto, W. Hiller, H. Schmidbaur, Chem. Ber. 126 (1993) 605.
[42] E. Delgado, E. Hernandez, Polyhedron 11 (1992) 3135.
´
[31] S. Kumar, S.H. Mashraqui, Indian J. Chem. 36B (1997) 656.
[32] P.R. Ashton, A. Chemin, C.G. Claessens, S. Menzer, J.F. Stoddart,
A.J.P. White, D.J. Williams, Eur. J. Org. Chem. (1998) 969.
[33] D.V. Demchuk, M.I. Lazareva, S.V. Lindeman, V.N. Khrustalyov,
Y.T. Struchkov, R.F. Ismagilov, E.I. Troyansky, G.I. Nikishin,
Synthesis (1995) 307.
[43] R.M. Davila, R.J. Staples, A. Elduque, M.M. Harlass, L. Kyle, J.P.
Fackler Jr., Inorg. Chem. 33 (1994) 5940.
[44] M.C. Gimeno, P.G. Jones, A. Laguna, M. Laguna, R. Terroba,
Inorg. Chem. 33 (1994) 3932.
[45] C.P. McArdle, M.C. Jennings, J.J. Vittal, R.J. Puddephatt, Chem.
Eur. J. 7 (2001) 3572.
´
[34] M. Preisenberger, A. Schier, H. Schmidbaur, J. Chem. Soc., Dalton
Trans. (1995) 1645.
[35] T.J. Hubin, D.H. Busch, Coord. Chem. Rev. 200–202 (2000) 5.
[36] P.R. Ashton, R. Ballardini, V. Balzani, S.E. Boyd, A. Credi, M.T.
[46] E. Cordova, R.A. Bissell, N. Spencer, P.R. Ashton, J.F. Stoddart,
A.E. Kaifer, J. Org. Chem. 58 (1993) 6550.
[47] (a) Computer programs COLLECT, DENZO, SCALEPACK, Nonius B.V.,
Amsterdam, 1998.;
´
´
Gandolfi, M. Gomez-Lopez, S. Iqbal, D. Philp, J.A. Preece, L.
(b) G.M. Sheldrick, SHELXTL-NT V6.1, Madison, WI, 2000.