Synthesis of luminescent trinuclear gold(I) derivatives with a triphosphine and S-donor ligands

Article abstract of DOI:10.1016/S0020-1693(01)00403-0

We have prepared a series of trinuclear gold(I) complexes containing bis(diphenylphosphinomethyl)phenylphosphine (dpmp) and several anionic S-donor ligands. The reaction of [(AuCl)₃(μ-dpmp)] with potassium ethyl xanthate afforded the trinuclear gold(I) complexes [Au₃Cl_3-x(S₂COEt)_x(μ-dpmp)] (x = 1, 2, 3). These complexes were readily transformed by reaction with silver triflate into [Au₃Cl_2-x(S₂COEt)_x(μ-dpmp)] (CF₃SO₃) (x = 1, 2). Treatment of [(AuCl)₃(μ-dpmp)] with sodium 2-pyridinthiolate or potassium thiocyanate led to complexes [Au₃Cl_3-x(2-SC₅H₄N)_x (μ-dpmp)] (x = 1, 3) and [{Au(SCN)}₃(μ-dpmp)]. The reaction of complex [Au₃Cl₂(S₂COEt)(μ-dpmp)] with sodium dithiocarbamate yielded [Au₃Cl(S₂CNR₂)(S₂COEt) (μ-dpmp)] (R = Me, CH₂Ph). We have studied the optical properties of these derivatives finding that most of them luminesce in the solid state at room temperature with emission maxima in the range 510-545, whilst at low temperature all are luminescent with emission maxima ranging from 480 to 545.

Full text of DOI:10.1016/S0020-1693(01)00403-0

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Inorganica Chimica Acta 318 (2001) 38–44
Synthesis of luminescent trinuclear gold(I) derivatives with a
triphosphine and S-donor ligands
Manuel Bardaj´ı, Antonio Laguna *
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received 10 November 2000; accepted 20 February 2001
Abstract
We have prepared a series of trinuclear gold(I) complexes containing bis(diphenylphosphinomethyl)phenylphosphine (dpmp)
and several anionic S-donor ligands. The reaction of [(AuCl)3(m-dpmp)] with potassium ethyl xanthate afforded the trinuclear
gold(I) complexes [Au3Cl3−x(S2COEt)x(m-dpmp)] (x=1, 2, 3). These complexes were readily transformed by reaction with silver
triflate into [Au3Cl2−x(S2COEt)x(m-dpmp)](CF3SO3) (x=1, 2). Treatment of [(AuCl)3(m-dpmp)] with sodium 2-pyridinthiolate or
potassium thiocyanate led to complexes [Au3Cl3−x(2-SC5H4N)x(m-dpmp)] (x=1, 3) and [{Au(SCN)}3(m-dpmp)]. The reaction of
complex [Au3Cl2(S2COEt)(m-dpmp)] with sodium dithiocarbamate yielded [Au3Cl(S2CNR2)(S2COEt)(m-dpmp)] (R=Me, CH2Ph).
We have studied the optical properties of these derivatives finding that most of them luminesce in the solid state at room
temperature with emission maxima in the range 510–545, whilst at low temperature all are luminescent with emission maxima
ranging from 480 to 545. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Gold complexes; Luminescent complexes; S-donor ligand complexes
luminescence, so the emission observed arises from a
sulfur to metal charge transfer excited state [3]. On the
1. Introduction
other hand, Fackler and co-workers showed that gold–
gold interactions can shift the emission maxima to
lower energies whilst Wang and co-workers described
concentration dependence of emission spectra due to
molecular aggregation through gold–gold interactions,
therefore mixing metal centred and ligand to metal
centred transitions are necessary to explain those cases
and gold–gold contacts are directly related to the lu-
minescence [4,5]. Moreover, Yam and co-workers have
designed a diphosphine-thiolate gold(I) complex able to
detect potassium ion [6].
In this paper we describe the synthesis of gold(I)
derivatives containing triphosphine bis(diphenylphos-
phinomethyl)phenylphosphine (dpmp) which allow the
formation of trinuclear derivatives combined with a
variety of S-donor ligands as xanthate (ꢀS2COR),
2-pyridinthiolate (2-SC5H4Nꢀ), thiocyanate and dithio-
carbamate. Luminescence studies of these complexes in
the solid state show that most are luminescent at room
temperature and all of them at 77 K.
There has been a great interest in the synthesis of
derivatives containing the P–Au(I)–S unit because they
are related to Auronafin, a drug used against the
rheumatoid arthritis [1]; besides, polynuclear derivatives
of this kind usually display gold–gold interactions
which have been rationalised in terms of correlation
and relativistic effects [2].
Recently, there have been reports about luminescent
gold(I) complexes, the P-donor ligand being a tertiary
mono- or diphosphine and the S-donor ligand a thio-
late, dithiolate (ꢀSRSꢀ), dithiocarbamate (ꢀS2CNR2),
xanthate (ꢀS2COR) or sulfide [3–11]. Some of them
have been used to try to understand the nature of the
emission. Bruce and co-workers reported that there is
no direct correlation between gold–gold distance and
* Corresponding author. Tel.: +34-976-761 185; fax: +34-976-
761 187.
E-mail address: alaguna@posta.unizar.es (A. Laguna).
0020-1693/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0020-1693(01)00403-0

M. Bardaj´ı, A. Laguna / Inorganica Chimica Acta 318 (2001) 38–44
39
2. Results and discussion
already contains the triphosphine dpmp as the bridging
ligand and that through substitution reactions of chlo-
ride by anionic S-donor ligands leads to the desired
products. The reaction of a suspension of this complex
with potassium ethyl xanthate in a mixture of dichloro-
methane–water in the appropriate molar ratio, evolves
with dissolution of the starting material to give a yellow
solution from which complexes 1–3 containing one,
two or three xanthate ligands can be isolated as yellow
solids (see Scheme 1). The coordinating chloride anion
in complexes 1 and 2 can be replaced by the non-coor-
dinating (for gold centres) triflate by using silver tri-
flate; in this way, we obtained complexes 4 and 5 as
yellow solids. A dichloromethane solution of 2 decom-
poses to give the insoluble polymeric [{Au(S2COEt)}n]
and the tetranuclear derivative [Au4Cl2(m-dpmp)2]-
(CF3SO3)2 whose X-ray structure has been already de-
scribed by us [12].
2.1. Syntheses and characterisation
We start with a trinuclear gold(I) derivative previ-
ously described by us [(AuCl)3(m-dpmp)] (dpmp=bis-
(diphenylphosphinomethyl)phenylphosphine)[12], which
These complexes are air- and moisture-stable solids
at room temperature. Their IR spectra show absorp-
tions at 335 and 325 (1), 322 (2) and 323 (4) cm−1 due
to w(AuꢀCl) [13] and at 1257, 1223 and 638 cm−1 from
triflate anions [14] (4 and 5). Their acetone solutions
behave close to 1:1 electrolytes for complexes 4 and 5
whilst the behaviour is non-conducting for the others
which implies that chloride is not acting as the counte-
rion (in complexes 1 and 2) as will be confirmed by the
NMR experiments as has been already reported for
other gold complexes with this triphosphine [15,16].
31P{1H} NMR chemical shifts and constant cou-
plings are summarised in Table 1. The 31P{1H} NMR
spectrum of 1 show an AB2 spin system which can be
explained by a structure with the xanthate bridging two
AuꢀPPh2 units and both chlorides bonded to the third
central gold centre; this tricoordination of the central
gold has been found for instance in [Au3Cl(m-
dpmp)2][PF6]2 [15]; the structure containing two
ClꢀAuꢀPPh2 units can be discarded because the chemi-
cal shift should be around 27 ppm as found in the
starting material or in other complexes in this work,
whilst a dichlorophosphine gold(I) derivative is low-
field shifted compared to a chlorophosphine gold(I)
derivative [17]. Besides, after removing a chloride to
obtain complex 4, the spectrum becomes more complex
showing a multiplet and a broad signal for two phos-
phorus. The low temperature spectra are very similar
for both complexes and show three resonances which
can be interpreted through a high field resonance due to
a ClꢀAuꢀPPh2 unit and xanthate bridging the other
gold centres; in this case the central phosphorus be-
comes chiral and therefore these complexes should be
racemic mixtures. This geometry can be in equilibrium
with its mirror image and with a structure containing
the xanthate bridging the two lateral gold centres and
thus we can explain the observed fluxionality at room
temperature for complex 4. The 31P{1H} NMR spec-
Scheme 1.
Table 1
31P{1H} NMR data in CHCl3-d solution a
Complex
l (18°C)
l (−55°C)
P1
P2
P3
P1
P2
P3
1
2
3
4
5
6
32.8
33.6
30.6
37.7
33.8
28.2 c
36.8
35.2
31.4
32.8
33.6
30.6
35.0
33.1
30.6 b
34.5
40.0
37.0
26.8
33.1
35–28 c
36.4
39.0
26.7
25.3
33.8
34.4–32.9 c
25.3
27.8 c
28.0
29.8
29.4 c
30.4
31.3
32.3
32.5
34.3
33.7
20.7
28.0 d
29.8 d
7
29.8
28.3
26.8
29.8
31.9
34.9
25.0
34.5
36.1
30.4 d
31.3
32.3
32.5
8
9
10
31.9
33.9 c
33.5 c
a P1, P2, P3 assigned as follows: P1 and P3 are the lateral phospho-
rus whereas P2 is the central one. Coupling constants and spin system
in Section 3.
b Ill-resolved.
c Broad signal that is not possible to assign to P1, P2, and P3.
d Measured in CD2Cl2 at −90°C.

40
M. Bardaj´ı, A. Laguna / Inorganica Chimica Acta 318 (2001) 38–44
(1)
These complexes are air- and moisture-stable yellow
solids at room temperature. Acetone solutions behave
as non-conductors and their IR spectra show absorp-
tions due to w(AuꢀCl) at 330 (6) cm−1 and at 2117 and
2079 cm−1 from thiocyanate (8). The 31P{1H} NMR
spectrum of 6 consist of a singlet, therefore a fluxional
process must be considered taking into account that
several rearrangements are possible by combining the
four additional donor atoms which can be bonded to
the gold centres. At −55°C there is an AX2 spin
system and still a broad resonance. At −90°C AX2 and
A2X spin systems are observed which we can tentatively
assign to structures containing a PPhꢀAuꢀS or a
PPhꢀAuꢀN unit, and two PPh2ꢀAuꢀCl units. The
31P{1H} NMR spectrum of 7 shows an A2B spin system
due to 2-pyridinthiolate bonded to each gold centre,
probably through the sulfur because gold is a soft
metal; curiously at −55°C the phosphorus atoms be-
come isochronous and only a singlet is seen although at
−90°C two resonances are observed separated by 3.6
ppm. In the 31P{1H} NMR spectrum of 8 an AB2 spin
system is observed as usually found in other gold–
dpmp systems [12,15,16]. Finally the 31P{1H} NMR
spectra of complexes 9 and 10 are not as for complex 2
as we could expect, but they show only a singlet,
although at −55°C an AB2 spin system is seen with
chemical shifts similar to those found in complex 2. In
Scheme 2.
trum of 2 shows an AB2 spin system and the non-con-
ducting behaviour in acetone solution does not permit
the assignment of a unique reasonable structure (l
(PPhꢀAuꢀCl) is expected around 23 ppm). After chang-
ing chloride by triflate, the chemical shifts move slightly
which points out again that there is not a chloro–gold–
phosphine unit in complex 2. The 31P{1H} NMR spec-
trum of 3 shows an AB2 spin system as expected for
1
one xanthate coordinated to each gold centre. The H
NMR spectra at room temperature involve two multi-
plets or two broad signals due to the four
diastereotopic methylene protons of the triphosphine at
approximately 4.8 and 4.1 ppm in the spectra of com-
plexes 1 and 2, around 4.4 and 4.2 ppm in the spectrum
of 3 and approximately 4.3 and 3.5 ppm in the spectra
1
the H NMR spectra the methylene protons of triphos-
phine are observed as two resonances around 4.6 and
4.1 ppm for complexes 9 and 10, as found in the
above-described complexes whilst only a signal in the
range 3.9–4.5 ppm is seen for complexes 6–8 (see
Section 3); the multiplet observed in the case of 8
becomes a singlet by doing a 1H{31P} NMR experi-
ment, which confirms that the four methylene protons
have the same chemical shift as already observed in
[Au4Cl2(m-dpmp)2](CF3SO3)2 [12]. The number of sig-
nals for the dithiocarbamate substituents is also impor-
of 4 and 5; in a H{31P} NMR experiment pseudoquar-
1
tets become doublets by coupling with the vicinal pro-
ton (see Section 3). The LSI MS show the peak
corresponding to [M−X]+ at m/z (complex, % abun-
dance, X): 1253 (1, 35, Cl; 4, 93, CF3SO3), 1339 (2, 85,
Cl; 3, 100, S2COEt; 5, 40, CF3SO3).
Treatment of our starting material [(AuCl)3(m-dpmp)]
with sodium 2-pyridinthiolate in
1
a
mixture of
tant in the H NMR but only a methyl resonance is
dichloromethane–ethanol in a 1:1 or 1:3 molar ratio
affords complexes 6 and 7 as yellow solids (see Scheme
2). The same procedure, but using potassium thio-
cyanate, leads to a white complex 8. We have tried to
carry out the same reaction with triphenylphosphine or
observed for 9 even at low temperature. The LSI MS
show the peak corresponding to [M−X]+ at m/z
(complex, % abundance, X): 1242 (6, 100, Cl), 1317 (7,
90, SC5H4N), 1213 (8, 100, SCN), 1338 (9, 100, Cl),
1490 (10, 65, Cl).
bis(diphenylphosphino)methane but
a
mixture of
chloro–gold–phosphine complexes containing each a
different phosphine are obtained instead of the mixed
triphosphine–monophosphine or diphosphine trinu-
clear derivatives. The reaction of complex 1 with
sodium dithiocarbamate affords complexes 9 and 10
containing ethyl xanthate and dithiocarbamate (see Eq.
(1))
2.2. Photophysical characterisation
The absorption spectra in dichloromethane was mea-
sured for all the complexes in the range 200–600 nm
(see Table 2). The spectra of complexes 1, 3, 7 and 8 are
plotted in Fig. 1. The main features are the following:
(a) an intense absorption at 230 nm due to phenyl

M. Bardaj´ı, A. Laguna / Inorganica Chimica Acta 318 (2001) 38–44
41
phosphine rings [18]; (b) a shoulder at 270 nm for
derivatives 2, 3, 7, 10 and more intense for the methyl
Table 2
Electronic absorption data for complexes 1–10 a
Complex
u/nm (10−3 m/M−1 cm−1
)
1
2
3
4
5
6
7
8
226 (54), 308 (18) b
229 (60), 272 (sh, 26), 310 (18) b
234 (54), 270 (sh, 24.5), 318 (35) b
230 (49), 311 (23) b
229 (56), 311 (22.5) b
229 (48.5) b
234 (47), 276 (sh, 28), 320 (sh, 14), 360(sh, 10.5) b
230 (47) c
9
10
230 (53.5), 270 (sh, 31.5), 312 (sh, 18.5) b
232 (49.5), 270 (30), 278 (30), 314 (sh, 23) b
Fig. 2. Excitation and emission spectra of complexes 6 (—) and 8
(- - - -) at room temperature in the solid state.
a In CH2Cl2 solution, 5×10−5 M.
b There is absorption up to 400 nm.
c There is absorption up to 350 nm.
dithiocarbamate derivative 9, and at 278 nm for the
benzyl dithiocarbamate derivative 10, which have been
previously assigned to these dithiocarbamate ligands
[5]; (c) an intense absorption centred in the range
310–318 nm was observed for xanthate derivatives 1–5,
9 and 10 due to this ligand [9]; (d) there is absorption
up to around 400 nm for all the complexes. These
shoulders can be assigned to sulfur to gold centred
transitions, to metal centred transitions or to a mixture
of both as reported for other phosphine–thiolate
gold(I) derivatives [5,11,19] and for trinuclear tris(phos-
phine) gold(I) derivatives [12,16,20]; even they have
been assigned to xanthate centred transitions [9].
The solid state emission and excitation spectra at 298
and 77 K have been determined and the results are
summarised in Table 3. The excitation and emission
spectra of complexes 6 and 8 at room temperature are
plotted in Fig. 2. Complexes 1, 2 and 6–10 luminesce at
room temperature, the maxima being located in the
range 510–545 nm, but only from 530 to 545 nm if we
do not consider the thiocyanate complex 8. The excita-
tion maxima are observed in a narrow range from 440
to 455 nm, except for complex 8 which is located at
400–415 nm.
Fig. 1. Absorption spectra in dichloromethane solution of complexes
1, 3, 7 and 8.
Table 3
Emission and excitation maxima (in nm) measured for complexes
1–10 at 298 and 77 K
Complex
Excitation
298 K
Emission
298 K
Excitation
77 K
Emission
77 K
The effect of exchanging the coordinating chloride
for the non-coordinating triflate is the loss of the
emission and also if all the chlorides are replaced by
xanthate ligands, which points out the importance of
this bridging chloride because of the tricoordinated
gold centre or because of the geometry adopted by the
metallic core. However, the replacement of all the chlo-
rides by thiocyanate or 2-pyridinthiolate evolves to
derivatives which show intense emissions; it is impor-
tant to note that the starting material does not lu-
minesce at room temperature [12]. It is clear that the
nature of the ligands bonded to the triphosphine trigold
1
440 (sh),
450
455
530 (sh),
540
540
395 (sh),
425
425
430
425
425
400 (sh),
420
385, 395,
415
375
535
2
3
4
5
6
540
540
535
535
530
440, 450
530
530
7
440, 450
(sh)
400, 415
455
520
8
9
10
510
545
535
480
535
545
415, 420
440, 450
455

42
M. Bardaj´ı, A. Laguna / Inorganica Chimica Acta 318 (2001) 38–44
core dramatically affects the luminescence properties
going from strong luminescent derivatives to non-emit-
ting solids.
ser. Melting points were measured on a Bu¨chi appara-
tus and left uncorrected. Conductivities were measured
in acetone solution with a Philips PW 9509 apparatus.
Mass spectra were recorded on a VG Autospec using
the LSI MS technique (with Cs gun) and 3-nitrobenzyl
alcohol as matrix. UV–Vis absorption spectra in
dichloromethane solution were recorded on a Unicam
UV–Vis 2. The luminescence spectra were recorded on
a Perkin–Elmer LS-50B spectrofluorometer.
At low temperature all the complexes are lumines-
cent, and in all cases much more intensely than at room
temperature, as expected because of the decrease of the
non-radiative thermal activated processes. The emission
maxima are blue shifted (approximately 30 nm for
complex 8, approximately 10 nm for 7 and 9) or red
shifted (approximately 10 nm for complex 10) versus
room temperature and are located in a very narrow
range from 520 to 545 nm, except again for complex 8
which is observed at 480 nm, probably because of the
different nature of the electronic transition involved.
Maxima in the excitation spectra are all blue shifted
versus room temperature. The effect of exchanging the
coordinating chloride for the non-coordinating triflate
does not affect the luminescence properties.
It is also important to note that dithiocarbamate,
thiocyanate and xanthate salts or the triphosphine
dpmp do not emit in the visible range. In luminescent
phosphine–thiolate gold(I) complexes, these emissions
have been assigned to LMCT transitions that in some
cases can be shifted by the gold–gold interactions, the
emission maxima being between 480 and 768 nm [3–
8,10,11]. On the other hand, the nature of luminescence
in most gold(I) complexes with a triphosphine or a
diphosphine have been described as related to metal–
metal interactions, therefore being MC transitions
[16,20,21].
3.2. Synthesis of [Au3Cl3−x(S2COEt)x(v-dpmp)]; x=1
(1), 2 (2), 3 (3)
To
a
dichloromethane suspension (20 cm3) of
[(AuCl)3(m-dpmp)] (0.12 g, 0.1 mmol) was added a
water (5 cm3) solution of KS2COEt (0.016 g, 0.1 mmol;
0.032 g, 0.2 mmol; 0.048 g, 0.3 mmol). Rapidly, the
solid was dissolved and the resulting yellow solution
was stirred for about 2 h. Then, the organic layer was
extracted, dried with anhydrous Na2SO4 and filtered.
Concentration to approximately 2 cm3 and addition of
diethyl ether (10 cm3) afforded 1 and 2 as white off
solids or 3 as a yellow solid, which were washed with
diethyl ether (2×5 cm3). Yield of 1: 103 mg (80%);
m.p. 270°C (dec.); \: 15.6 V−1 cm2 mol−1. 1H NMR: l
8.1–6.9 (m, 25H, Ph), 4.79 (‘q’, 2H, J=12.3 Hz,
PꢀCH2ꢀP), 4.67 (q, 2H, 3J(HH)=6.3 Hz, CH2ꢀO), 4.06
(‘q’, 2H, J=9.0 Hz, PꢀCH2ꢀP), 1.49 (t, 3H, CH3);
1H{31P} NMR: l 8.1–6.9 (m, 25H, Ph), 4.78 (d, 2H,
3
2J(HH)=12.0 Hz, PꢀCH2ꢀP), 4.67 (q, 2H, J(HH)=
However, the narrow emission maxima range found
for complexes 1–7 and 9–10, containing varying
amounts of different S-donor ligands can be interpreted
as a ligand based transition or still better a metal-per-
turbed intraligand transition which should be mainly
centred in the common triphosphine ligand as previ-
ously described for some halo–phosphine–gold(I),
phosphine–sulfide–gold(I) or phosphine–xanthate–
gold(I) complexes [9,11,22].
6.3 Hz, CH2ꢀO), 4.06 (br, 2H, PꢀCH2ꢀP), 1.49 (t, 3H,
CH3); 31P{1H} NMR: l 36.8, 32.8, AB2 spin system
2
1
with JAB=66 Hz; H NMR (−55°C): l 8.2–6.9 (m,
25H, Ph), 4.78 (br, 4H, PꢀCH2ꢀP), 4.55 (br, 2H,
CH2ꢀO), 1.45 (br, 3H, CH3); 31P{1H} NMR (−55°C):
l 40.0 (br), 35.0 (br), 26.8 (br). Anal. Found: C, 32.2;
H, 2.5; S, 4.75. Calc. for C35H34Au3Cl2OP3S2: C, 32.6;
H, 2.65; S, 4.95%. LSI MS; m/z (%, M+): 1253 (35,
[M−Cl]+). Yield of 2: 96 mg (70%); m.p. 225°C (dec.);
1
\: 17.2 V−1 cm2 mol−1. H NMR: l 8.1–6.9 (m, 25H,
Ph), 4.75 (br, 2H, PꢀCH2ꢀP), 4.61 (q, 4H, 3J(HH)=6.3
Hz, CH2ꢀO), 4.12 (br, 2H, PꢀCH2ꢀP), 1.45 (t, 6H,
3. Experimental
1
CH3); H{31P} NMR: l 8.1–6.9 (m, 25H, Ph), 4.73 (d,
3.1. General
2H, 2J(HH)=13.6 Hz, PꢀCH2ꢀP), 4.56 (q, 4H,
3J(HH)=6.3 Hz, CH2ꢀO), 4.12 (d, 2H, PꢀCH2ꢀP), 1.40
(t, 6H, CH3); 31P{1H} NMR: l 35.2, 33.6; AB2 spin
All the reactions were carried out under an argon
atmosphere at room temperature. The IR spectra were
recorded on a Perkin–Elmer 883 spectrophotometer,
over the range 4000–200 cm−1, by using Nujol mulls
between polyethylene sheets. 1H, 1H{31P}, 19F and
31P{1H} NMR spectra were recorded on a Bruker ARX
300 or GEMINI 2000 apparatus in CHCl3-d solutions
(if no other solvent is stated); chemical shifts are quoted
2
1
system with JAB=70 Hz. H NMR (−55°C): l 8.1–
6.9 (m, Ph), 4.53 (br, CH2ꢀO+PꢀCH2ꢀP), 1.43 (br,
CH3); 31P{1H} NMR (−55°C): l 37.0 (br, 1P), 33.1
(br, 2P). Anal. Found: C, 32.8; H, 2.9; S, 9.05. Calc. for
C38H39Au3ClO2P3S4: C, 33.2; H, 2.85; S, 9.35%. LSI
MS; m/z (%, M+): 1339 (85, [M−Cl]+), 1021 (100,
[M−Au−Cl−S2COEt]+). Yield of 3: 117 mg (80%);
1
1
relative to SiMe4 (external, H), CFCl3 (external, 19F)
m.p. 180 °C (dec.); \: 10.2 V−1 cm2 mol−1. H NMR:
and 85% H3PO4 (external, 31P). C, H, N and S analyses
l 7.9–6.9 (m, 25H, Ph), 4.47 (q, 8H, J(HH)=7.1 Hz,
3
were performed with a Perkin–Elmer 2400 microanaly-
CH2ꢀO+PꢀCH2ꢀP as shoulder), 4.23 (br, 2H,

M. Bardaj´ı, A. Laguna / Inorganica Chimica Acta 318 (2001) 38–44
43
PꢀCH2ꢀP), 1.30 (t, 9H, CH3); 31P{1H} NMR: l 31.4,
30.6; AB2 spin system with 2JAB=70 Hz. 1H NMR
(−55°C): l 7.8–6.6 (m, Ph), 4.44 (br, PꢀCH2ꢀP), 4.23
(br, CH2ꢀO), 3.95 (br, PꢀCH2ꢀP), 1.07 (br, CH3);
31P{1H} NMR (−55°C): l 30.6 (br). Anal. Found: C,
33.4; H, 2.9; S, 13.05. Calc. for C41H44Au3O3P3S6: C,
33.7; H, 3.05; S, 13.15%. LSI MS; m/z (%, M+): 1339
(100, [M−S2COEt]+).
ethanol solution (5 cm3) of potassium pyridin-2-thiolate
(0.1 or 0.3 mmol; prepared in situ from C5H5NS and
KOH/EtOH). Rapidly, the solid was dissolved and the
resulting yellow solution was stirred for about 2 h.
Then filtered through celite and concentrated to ap-
proximately 2 cm3. Addition of diethyl ether (10 cm3)
afforded 6–7 as white solids, which were washed with
diethyl ether (2×5 cm3). Yield of 6: 109 mg (85%);
m.p. 170°C (dec.); \: 20.1 V−1 cm2 mol−1. 1H NMR: l
8.44 (s, 1H, C5H4NS), 7.8–6.9 (m, 28H, Ph and
C5H4NS), 4.48 (brs, 4H, PꢀCH2ꢀP); 31P{1H} NMR: l
28.2 (s). 1H NMR (−55°C): l 8.4–6.9 (m, 29H, Ph and
3.3. Synthesis of [Au3Cl2−x(S2COEt)x(v-dpmp)]-
CF3SO3; x=1 (4), 2 (5)
To a dichloromethane solution (20 cm3) of 1 (64 mg,
0.05 mmol) or 2 (69 mg, 0.05 mmol) was added
AgCF3SO3 (13 mg, 0.05 mmol). The mixture was
stirred for about 2 h protected from light, then filtered
through celite and concentrated to approximately 2
cm3. Addition of diethyl ether (20 cm3) afforded 4 and
5 as yellow solids, which were washed with diethyl ether
(2×5 cm3). Yield of 4: 48 mg (68%); m.p. 280°C (dec.);
C5H4NS), 5.01 (br, 2H, PꢀCH2ꢀP), 3.57 (br, 2H,
2
PꢀCH2ꢀP); 31P{1H} NMR (−55°C): l 34.3 (t, JPP
=
64.3 Hz, 1P), 27.8 (br, 2P), 25.3 (d, 2P). 31P{1H} NMR
(−90°C, CH2Cl2-d2): l 33.7 (t, 2JPP=75.7 Hz, 1P),
2
29.8 (d, JPP=72.9 Hz, 2P), 28.0 (d, 2P), 20.7 (t, 1P).
Anal. Found: C, 34.55; H, 2.6; N: 1.1; S, 2.5. Calc. for
C37H33Au3Cl2NP3S: C, 34.75; H, 2.6; N, 1.1; S, 2.5%.
LSI MS; m/z (%, M+): 1242 (100, [M−Cl]+). Yield of
1
\: 91.5 V−1 cm2 mol−1. H NMR: l 7.8–6.9 (m, 25H,
7: 110 (77%); m.p. 130°C (dec.); \: 41.5
3
1
Ph), 4.72 (q, 2H, J(HH)=6.8 Hz, CH2ꢀO), 4.35 (‘q’,
V
−1 cm2 mol−1. H NMR: l 8.2–6.7 (m, 37H, Ph and
2H, J=13.2 Hz, PꢀCH2ꢀP), 3.51 (br, 2H, PꢀCH2ꢀP),
C5H4NS), 4.54 (m, 4H, PꢀCH2ꢀP); 31P{1H} NMR: l
2 1
1
1.54 (t, 3H, CH3); H{31P} NMR: l 7.8–6.9 (m, 25H,
29.8, 28.3; A2B spin system with JAB=66.8 Hz. H
NMR (−55°C): l 8.4–6.7 (m, Ph and C5H4NS), 5.57,
5.01, 4.56, 4.28 (br, PꢀCH2ꢀP); 31P{1H} NMR (−
55°C): l 29.4. 31P{1H} NMR (−90°C, CH2Cl2-d2): l
34.9 (br, 1P), 30.4 (br, 2P). Anal. Found: C, 39.4; H,
2.85; N, 2.9; S, 6.75. Calc. for C47H41Au3N3P3S3: C,
39.55; H, 2.9; N, 2.95; S, 6.75%. LSI MS; m/z (%, M+):
1010 (100, [M−Au−2SC5H4]+), 1317 (90, [M−
SC5H4]+).
3
Ph), 4.72 (q, 2H, J(HH)=6.8 Hz, CH2ꢀO), 4.35 (d,
2H, 2J(HH)=14.8 Hz, PꢀCH2ꢀP), 3.48 (br, 2H,
PꢀCH2ꢀP), 1.54 (t, 3H, CH3); 31P{1H} NMR: l 37.7
1
(m, 1P), 35–28 (br, 2P); H NMR (−55°C): l 7.9–6.9
(m, 25H, Ph), 4.68 (br, 2H, CH2ꢀO), 4.48 (br, 2H,
PꢀCH2ꢀP), 4.03 (br, 2H, PꢀCH2ꢀP), 1.47 (br, 3H, CH3);
31P{1H} NMR (−55°C): l 39.0, 34.5, 26.7, ABX spin
2
2
4
system with JAB=65.5 Hz, JAX=45.0 Hz, JBX=0.
Anal. Found: C, 30.5; H, 2.35; S, 6.55. Calc. for
C36H34Au3ClF3O4P3S3: C, 30.8; H, 2.45, S: 6.85%. LSI
MS; m/z (%, M+): 1253 (92, [M−CF3SO3]+). Yield of
5: 65 mg (87%); m.p. 252°C (dec.); \: 93.6
3.5. Synthesis of [{Au(SCN)}3(v-dpmp)] (8)
V
−1 cm2 mol−1
4.61 (q, 4H, J(HH)=6.3 Hz, CH2ꢀO), 4.31 (‘q’, 2H,
.
1H NMR: l 7.8–6.9 (m, 25H, Ph),
3
To a
dichloromethane suspension (20 cm3) of
J=12.4 Hz, PꢀCH2ꢀP), 3.49 (‘q’, 2H, J=12.1 Hz,
[(AuCl)3(m-dpmp)] (0.12 g, 0.1 mmol) was added a
water (5 cm3) solution of KSCN (0.029 g, 0.3 mmol).
Rapidly, the solid was dissolved and the resulting clear
solution was stirred for about 2 h. Then the organic
layer was extracted, dried with anhydrous Na2SO4 and
filtered. Concentration to approximately 2 cm3 and
addition of diethyl ether (10 cm3) afforded complex 8 as
a white solid, which was washed with diethyl ether
(2×5 cm3). Yield: 121 mg (95%); m.p. 130°C (dec.); \:
PꢀCH2ꢀP), 1.47 (t, 6H, CH3); H{31P} NMR: l 7.8–6.9
1
3
(m, 25H, Ph), 4.62 (q, 4H, J(HH)=6.2 Hz, CH2ꢀO),
2
4.27 (d, 2H, J(HH)=14.6 Hz, PꢀCH2ꢀP), 3.46 (d, 2H,
PꢀCH2ꢀP), 1.47 (t, 6H, CH3); 31P{1H} NMR: l 36.4
1
(m, 1P), 33.8 (br, 2P); H NMR (−55°C): l 7.8–6.9
(m, Ph), 4.6–4.2 (brm, CH2ꢀO+PꢀCH2ꢀP), 1.43 (br,
CH3); 31P{1H} NMR (−55°C): l 34.4–32.9 (brm).
Anal. Found: C, 31.15; H, 2.55; S, 10.4. Calc. for
C39H39Au3F3O5P3S5: C, 31.45; H, 2.65; S, 10.75%. LSI
MS; m/z (%, M+): 1339 (40, [M−CF3SO3]+), 1021
(100, [M−Au−Cl−S2COEt]+).
11.9 V−1 cm2 mol−1
.
1H NMR: l 7.7–7.0 (m, 25H,
1
Ph), 3.88 (‘q’, 4H, J=9.9 Hz, CH2ꢀP); H{31P} NMR
7.7–7.0 (m, 25H, Ph), 3.83 (s, 4H, CH2ꢀP); 31P{1H}
NMR: l 31.9 (d, J=67.5 Hz), 26.8t. H NMR (−
1
3.4. Synthesis of [Au3Cl3−x(2-SC5H4N)x(v-dpmp)];
x=1 (6), 3 (7)
55°C): l 7.8–6.8 (m, Ph), 4.6–3.6 (br, PꢀCH2ꢀP);
31P{1H} NMR (−55°C): l 31.3 (br, 2P), 25.0 (br, 1P).
Anal. Found: C, 33.1; H, 2.0; N, 3.2; S, 7.5. Calc. for
C35H29Au3N3P3S3: C, 33.05; H, 2.3; N, 3.3; S, 7.55%.
LSI MS; m/z (%, M+): 1213 (100, [M−SCN]+).
To
[(AuCl)3(m-dpmp)] (0.12 g, 0.1 mmol) was added an
a
dichloromethane suspension (20 cm3) of

44
M. Bardaj´ı, A. Laguna / Inorganica Chimica Acta 318 (2001) 38–44
3.6. Synthesis of [Au3Cl(S2CNR2)(S2COEt)(v-dpmp)];
R=Me (9), CH2Ph (10)
financial support. We also thank Dr. J. Galba´n (Uni-
versidad de Zaragoza, Spain) for helpful discussions.
To a dichloromethane solution (10 cm3) of 1 (64 mg,
0.05 mmol) was added NaS2CNR2 (0.05 mmol; R=Me
7 mg, CH2Ph 15 mg). The mixture was stirred for about
2 h, then filtered through celite and concentrated to
approximately 2 cm3. Addition of diethyl ether (15 cm3)
afforded 9 and 10 as yellow solids, which were washed
with diethyl ether (2×5 cm3). Yield of 9: 60 mg (88%);
m.p. 165°C (dec.); \: 40.6 V−1 cm2 mol−1. 1H NMR: l
8.1–6.9 (m, 25H, Ph), 4.65 (br, 2H, PꢀCH2ꢀP), 4.53 (q,
2H, 3J(HH)=7.0 Hz, CH2ꢀO), 4.07 (br, 2H,
PꢀCH2ꢀP), 3.62 (s, 6H, Me), 1.37 (t, 3H, CH3ꢀCH2);
31P{1H} NMR: l 33.9 (br); 1H NMR (−55°C): l
8.1–6.8 (m, 25H, Ph), 4.56 (br, 4H, PꢀCH2ꢀP and
CH2ꢀO), 3.75 (br, 2H, PꢀCH2ꢀP), 3.53 (s, 6H, Me),
1.34 (br, 3H, CH3ꢀCH2); 31P{1H} NMR (−55°C): l
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34.5, 32.3, AB2 spin system with JAB=72.2 Hz. Anal.
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C38H40Au3ClNOP3S4: C, 33.2; H, 2.95; N, 1.0; S,
9.35%. LSI MS; m/z (%, M+): 1338 (100, [M−Cl]+).
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V
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PꢀCH2ꢀP), 1.25 (t, 3H, CH3ꢀCH2); 31P{1H} NMR: l
33.5 (br); 1H NMR (−55°C): l 8.1–6.8 (m, Ph),
5.2–3.8 (m, NꢀCH2Ph, PꢀCH2ꢀP and CH2ꢀO), 1.15
(br, CH3ꢀCH2); 31P{1H} NMR (−55°C): l 36.1,
32.5, AB2 spin system with 2JAB=81.6 Hz. Anal.
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C50H48Au3ClNOP3S4: C, 39.35; H, 3.15; N, 0.9; S,
8.4%. LSI MS; m/z (%, M+): 1490 (65,
[M−Cl]+).
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Acknowledgements
We thank the Direccio´n General de Investigacio´n
Cient´ıfica y Te´cnica (Project PB97-1010-C02-01) for
.