Mesityl gold(III) complexes. X-ray structure of mononuclear [Au(mes)2Cl(PPh3)] and the dimer [Au(mes)2Cl]2

Article abstract of DOI:10.1016/S0022-328X(00)00306-5

The reaction between PPN[AuCl₄] and [Hg(mes)₂] gives the anionic complex cis-PPN[Au(mes)₂Cl₂] (1) and [Hg(mes)Cl] as side-product. Complex 1 is a precursor to other compounds both neutral and cationic. Removal o

Full text of DOI:10.1016/S0022-328X(00)00306-5

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 607 (2000) 129–136
Mesityl gold(III) complexes. X-ray structure of mononuclear
[Au(mes)2Cl(PPh3)] and the dimer [Au(mes)2Cl]2
Mar´ıa Contel a,d, Andrew J. Edwards b, Julia´n Garrido a, Michael B. Hursthouse c,
Mariano Laguna d,*, Raquel Terroba c
a Departamento de Qu´ımica Aplicada, Uni6ersidad Pu´blica de Na6arra, E-31006 Pamplona, Spain
b Department of Chemistry, Uni6ersity of Newcastle, Newcastle upon Tyne, NE1 7RU, UK
c Department of Chemistry, Uni6ersity of Southampton Highfield, Southampton, SO17 1BJ, UK
d Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza C.S.I.C.,
E-50009 Zaragoza, Spain
Received 17 March 2000; received in revised form 5 May 2000; accepted 15 May 2000
Dedicated to Prof. Martin A. Bennett in recognition of his outstanding contributions to organometallic and inorganic chemistry, on the
occasion of his 65th birthday.
Abstract
The reaction between PPN[AuCl4] and [Hg(mes)2] gives the anionic complex cis-PPN[Au(mes)2Cl2] (1) and [Hg(mes)Cl] as
side-product. Complex 1 is a precursor to other compounds both neutral and cationic. Removal of one chloride ligand affords
the mononuclear neutral complexes cis-[Au(mes)2ClL] (L=PPh3 (2), P{p-tol}3 (3), AsPh3 (4), SPPh3 (5)) by addition of a neutral
ligand or, alternatively if no ligand is added, dimeric cis-[Au(mes)2Cl]2 (6). If both chloride groups in 1 are removed, cationic
compounds can be obtained by addition of a potentially bidentate ligand affording cis-[Au(mes)2(L–L)]X complexes (X=ClO4,
L–L=bipy (7), L–L=phen (8), L–L=dppe (9) X=SO3CF3, L–L=dppm (10)). Dithiocarbamate- or acetate salts can be
added to solutions of ‘Au(mes)2X’ (obtained by removal of two chloride anions in 1) leading to the neutral compounds
cis-[Au(mes)2(L–L)] (L–L=S2CNR2 (R=Me (11), Et (12), Bz (13)), O2CCF3 (14)). The structures of cis-[Au(mes)2Cl(PPh3)] (2)
and cis-[Au(mes)2Cl]2 (6) have been established by an X-ray diffraction study. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Gold(III); Mercury; Mesityl
We have been reporting on the chemistry of mesityl
gold(I) derivatives [11–13]. The radical mesityl
1. Introduction
[(C6H2Me3)–] can act as a simple (terminal) ligand or
Gold(III) complexes with two gold-carbon bonds
as a bridge between two metalic centres affording a
have been known for a long time, particularly those
three-centre two-electron bond. Mesityl gold(I) deriva-
containing methyl or pentafluorophenyl groups as lig-
tives of the type [AuRL] have proven to be useful
ands [1–4]. The traditional synthesis with Grignard or
precursors to homo- and hetero-polynuclear com-
organolithium reagents lead generally to very low
yields. Improved synthetic methods involved the use of
pounds [11,12] that have displayed interesting metal-
metal interactions. We wanted to extend this chemistry
organotin [5], organothalium [6] and organomercury
to gold(III) complexes and study the behaviour of such
[7,8] reagents or, in a few cases, the oxidative addition
compounds.
of halogen to the corresponding organogold(I) com-
Gold(III) componds containing the mesityl group as
a terminal ligand have been obtained by reaction be-
plexes [AuR2]− [9,10].
tween the Grignard reagent and [AuCl2(L–L)]ClO4 [L–
L=bipy (2,2%-bipyridine), phen (1,10-phenantroline),
dpphen (4,7-diphenylphenantroline)] [14] and by oxida-
tive addition of halogens to mesityl gold(I)
* Corresponding author. Tel.: +34-767-61181; fax: +34-767-
61187.
E-mail address: mlaguna@posta.unizar.es (M. Laguna).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00306-5

130
M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
Q[Au(mes)X]
complexes
(Q=P(CH2Ph)PPh3,
Both compounds are easily separated and purified by
N(PPh3)2) [11]. However, both methods have restric-
tions. The first one is limited by the range of available
gold(III) starting materials stable towards the derivative
Mg(mes)Br. The second only affords gold(III) com-
plexes with one mesityl group. It was, therefore, desir-
able to obtain a mesityl gold(III) compound that could
be used as a precursor to other gold(III) products in a
wider range.
In this paper we describe the synthesis of the com-
pound cis-PPN[Au(mes)2Cl2] (1) (PPN+: N(PPh3)2,
bis(triphenylphosphine)iminium)) which is obtained via
the organomercury reagent [Hg(mes)2] [15] according to
an earlier procedure for transferring one or two aryl
groups to gold(III) centres [7,8,16–24]. Attempts to
prepare 1 via Grignard or lithiated reagents and
PPN[AuCl4] failed due to predominant reduction to
PPN[Au(mes)Cl] previously reported [11]. Complex 1
behaves as a precursor to other mesityl gold(III) com-
pounds both neutral and cationic.
fractional crystallization. Attempts to substitute more
chloride anions by mesityl groups following the method
described in Scheme 1(i) failed. This behaviour is simi-
lar to what Vicente et al. found for the reaction be-
tween HgR2 (R=ortho-nitro aryl groups) and
Q[AuCl4] [7,8]. This method only leads to the formation
of Q[AuR2Cl2].
Removal of one chloride group from 1 is achieved by
reaction of 1 and silver triflate or silver perchlorate in a
dichloromethane–OEt2 solution. Neutral complexes are
obtained by addition of L=PPh3 (2), P{p-tol}3 (3),
AsPh3 (4), SPPh3 (5) in a 1:1 ratio to solutions of
‘Au(mes)2Cl’ (Scheme 1(iv)). If no ligand is added to
these solutions dimeric [Au(mes)2Cl]2 (6) precipitates
after subsequent treatment of the filtrate (Scheme 1(v)).
By using two equivalents of silver triflate or silver
perchlorate the two chloride anions present in 1 can be
removed (Scheme 1(iii)). Proposed [Au(mes)2S(X)]
(S=solvent molecule, X=OClO3, OSO2CF3) failed to
be isolated due to, presumably, their inestability.
However, addition of bidentate ligands such as di-
amines or diphosphines [L–L=bipy, phen, dppe
(1,2-bis(diphenylphosphino)ethane), or dppm (1,2-bis-
(diphenylphosphino)methane)] stabilises the ‘Au-
(mes)2SX’ species by formation of square-planar
cationic complexes of the type [Au(mes)2(L–L)]X
(Scheme 1(vi)). Compounds 7 and 8 (with bipy and
phen, respectively) had been previously synthesised by
2. Results and discussion
The reaction in refluxing acetone of PPN[AuCl4] with
Hg(mes)2 in a molar ratio 1:2 for 10 h leads to the
formation of cis-PPN[Au(mes)2Cl2] (1) together with
[Hg(mes)Cl] in high yield (Scheme 1(i)).
Scheme 1. (i) (1:2) Molar ratio, D, acetone, –[Hg(mes)Cl]; (ii) AgX (1:1); –AgCl, –PPNCl; (iii) AgX (1:2), –2AgCl, –PPNCl; (iv) L; (v) n-hexane;
(vi) L–L; (vii) Q(L–L), –QX.

M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
131
Table 1
Spectroscopic and conductivity data for compexes 1–14
a
Complex
31P{1H}-NMR
1H-NMR a
LM b
o-Me
p-Me
m-H
Other
1 cis-PPN[Au(mes)2Cl2]
–
2.49 (s)
2.05 (s)
6.49 (s)
–
–
132
3
4
9
1
2 cis-[Au(mes)2Cl(PPh3)]
3 cis-[Au(mes)2Cl(P{p-tol}3)]
4 cis-[Au(mes)2Cl(AsPh3)]
5 cis-[Au(mes)2Cl(SPPh3)]
6 cis-[Au(mes)2Cl]2
7 cis-[Au(mes)2(bipy)]ClO4
8 cis-[Au(mes)2(phen)]ClO4
9 cis-[Au(mes)2(dppe)]ClO4
10 cis-[Au(mes)2(dppm)]TfO
11 cis-[Au(mes)2(S2CNMe2)]
12 cis-[Au(mes)2(S2CNEt2)]
27.8 (s)
26.6 (s)
2.47 (s), 2.07 (s)
2.47 (s), 2.07 (s)
2.49 (s), 2.16 (s)
2.31 (s), 2.14 (s)
2.53 (s)
2.32 (s)
2.37 (s)
1.84 (s)
2.05 (s)
2.12 (s), 2.04 (s)
2.12 (s), 2.04 (s)
2.13 (s), 2.05 (s)
2.53 (s), 2.05 (s)
2.13 (s)
2.26 (s)
2.29 (s)
2.13 (s)
2.18 (s)
6.65 (d) c, 6.31 (s)
6.64 (d) d, 6.28 (s)
6.64 (s), 6.34 (s)
6.56 (s, br), 6.46 (s)
6.58 (s)
2.35(s) e
–
–
–
43.9 (s)
–
–
–
–
7
f
6.80 (s)
131
128
127
110
2
g
6.85 (s)
45.1 (s)
6.55 (d) h
3.24 (‘d’) i
5.61 (t) j
3.29 (s) k
3.68 (q) l
1.31 (t) m
4.78 (s) n
–
−25.5 (s)
–
–
6.66 (s, br)
6.63 (s)
6.63 (s)
2.48 (s)
2.49 (s)
2.15 (s)
2.15 (s)
20
13 cis-[Au(mes)2(S2CNBz2)]
14 cis-[Au(mes)2(O2CCF3)]
–
–
2.54 (s)
2.43 (s)
2.16 (s)
2.18 (s)
6.66 (s)
6.63 (s)
15
2
a In CDCl3, values in ppm.
b In acetone (5×10−4 mol l−1).
c [5JP–H=3.9 Hz].
d [5JP–H=3.9 Hz].
e P(p-C6H4CH3)3.
f L=bipy 8.97 (dd) Hd, 8.47 (td) Hc, 7.84 (dd) Hb, 7.72 (td) Ha.
g L=phen, 9.05 (H2, H9), 8.35 (H5, H6), 8.23 (H7, H4), 8.09 (H3), 8.07 (H8).
h [5JP–H=3.7 Hz].
i L=Ph2P–CH2CH2–PPh2, [2JP–H=16.8 Hz].
j L=Ph2P–CH2–PPh2, [2JP–H=10.8 Hz].
k L=SCN(CH3)2.
l –CH2, [3JH–H=10.8 Hz].
m –CH3, [3JH–H=7.18 Hz].
n –CH2–C6H5.
absorptions at 291 (s) and 278 (s) that can be assigned
to two active bands w (Au–Cl) (a1, b1) of the cis-isomer
(C2v symmetry).
reaction of [AuCl2(L–L)]ClO4 and Mg(mes)Br in a
1:2.5 molar ratio [14].
The filtrates containing ‘Au(mes)2X’ species can be
treated with sodium dithiocarbamates (Na[S2CNR2]
(R=Me, Et and Bz)) or with [MePPh3]CF3COO to
afford neutral complexes [Au(mes)2(L–L)] and salts of
the type QX (Q=Na or MePPh3, X=CF3SO3) as
side-products (Scheme 1(vii)).
All the gold(III) mesityl products described in this
paper are stable in the solid state or in dichloromethane
solution at room temperature. They are obtained as
white or pale yellow solids. Acetone solutions of 1,
7–10 display conductivities typical of 1:1 electrolytes
whereas 2–6 and 11–14 are non-conducting (Table 1).
Compounds 3–6, 8, 11–14 are partly soluble in sol-
vents such as Et2O or n-hexane and they are obtained
in yields of ca. 50%.
The IR spectra (see Section 3) show absorptions from
the mesityl ligand for all the compounds. In the case of
anionic or cationic complexes signals that can be as-
signed to the PPN cation (1), anionic ClO4 [25] (7–9) or
TfO [26] (10) can be observed. The IR spectra of the
starting material cis-PPN[Au(mes)2Cl2] (1) shows two
Their 1H-NMR spectra (Table 1) are as expected
showing three signals due to the mesityl ligand (protons
from the ortho- and para-methyl groups and protons in
meta). In the case of the complexes [Au(mes)2ClL]
(2–5) signals that belong to two different mesityl
groups (in cis or trans to the entering ligand) can be
observed. For the phosphine complexes (2 and 3) the
assigned signal for m-H of one mesityl group is ob-
served as a doublet (5JP–H=3.9 Hz, Table 1) due to the
coupling with the phosphine in trans. All these data
together with the structural determination by means of
an X-ray analysis of complex 2 (vide infra) is consistent
with the proposal of square-planar complexes 2–5 be-
ing the cis isomers. The signals assigned to the mesityl
ligand in the 1H-NMR spectra of the neutral com-
pounds 7–14 are very similar to those found for 1.
The 31P{1H}-NMR of the compounds containing
bidentate phosphines (9 and 10) shows a singlet but at
very different chemical shifts (Table 1). In the case of 9
(L–L=dppe) the signal appears at l 45.1 ppm (consis-

132
M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
Fig. 1. Molecule of compound 2 in the crystal. Displacement parameter ellipsoids represent 50% probability surfaces. H atoms are omitted for
clarity.
tent with two phosphorus atoms coordinated to a
gold(III) centre). For 10 (L–L=dppm) the resonance
is highly shielded (l −25.5 ppm) and explained on the
basis of the constrain imposed on the four-membered
phosphorus chelate ring as described for other metallic
complexes [27].
In the case of the complexes with bidentate ligands
the spectroscopic data indicates a cis-configuration and
the mass spectra data points to the monomeric nature
of these compounds. Furthermore, the crystal structure
of 7, that had been reported earlier, [14] confirmed such
a cis-configuration. It is noteworthy how, in the case of
the complexes with one monodentate ligand (2–6), the
spectroscopic data also indicates such a cis-configura-
tion. It seems reasonable to have foreseen a trans
disposition for the mesityl groups since it would be
sterically more favourable. In order to confirm the
results in solution, single crystal X-ray diffraction stud-
ies of compounds 2 and 6 were carried out.
compare these Au–C distances to those reported for
gold(I)–mesityl complexes there are similar variations.
In the case of [Ag(m-dppm)2{Au(mes)}2]ClO4 [13] dis-
,
tances of 2.083(10) and 2.080(9) A have been reported
being shorter than those found in the anionic deriva-
,
tives [N(PPh3)2][(mes)AuCNAu(mes)] (2.035(11) A) [28]
,
and [NEt4][AuCl(mes)] (2.018(7) A) [28]. The cis-
mesityl groups are disposed perpendicularly to the co-
Table 2
,
Bond lengths (A) and angles (°) for 2
Bond lengths
Au(1)–C(1)
Au(1)–Cl(1)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(04)
C(6)–C(06)
P(1)–C(41)
2.062(8)
2.381(2)
1.326(11)
1.390(11)
1.375(11)
1.526(11)
1.516(11)
1.828(8)
Au(1)–C(11)
Au(1)–P(1)
C(1)–C(6)
C(2)–C(02)
C(4)–C(5)
C(5)–C(6)
2.070(7)
2.423(2)
1.461(11)
1.507(11)
1.376(11)
1.357(11)
The molecular structure of 2 is shown in Fig. 1 and
selected bond distances and angles are given in Table 2.
The gold atom is in an almost square-planar environ-
ment with the mesityl ligands in a cis disposition. The
Bond angles
C(1)–Au(1)–C(11)
C(11)–Au(1)–Cl(1)
C(11)–Au(1)–P(1)
C(2)–C(1)–C(6)
C(6)–C(1)–Au(1)
C(1)–C(2)–C(02)
C(4)–C(3)–C(2)
C(3)–C(4)–C(04)
C(6)–C(5)–C(4)
C(5)–C(6)–C(06)
89.7(3)
89.1(2)
C(1)–Au(1)–Cl(1) 172.3(2)
C(1)–Au(1)–P(1)
Cl(1)–Au(1)–P(1)
92.7(2)
90.05(8)
168.1(2)
120.2(8)
113.9(6)
121.7(8)
121.7(8)
120.8(8)
123.6(8)
120.1(8)
,
gold(III)-Cipso distances are 2.062(8) and 2.070(7) A, a
C(2)–C(1)–Au(1) 125.9(7)
little bit longer than those described for
C(1)– C(2)–C(3)
C(3)–C(2)–C(02)
C(3)–C(4)–C(5)
C(5)–C(4)–C(04)
C(5)–C(6)–C(1)
C(1)–C(6)–C(06)
120.3(8)
118.1(7)
117.4(8)
121.7(8)
116.6(8)
123.2(7)
,
[Au(mes)2(bipy)]ClO4 (7) (2.020(5), 2.029(6) A) [14], the
only gold(III) mesityl complexes to be structurally char-
acterised up to date. These Au–C distances are also
slightly longer than those found in the bis(mesityl)
complex 6 reported is this article (vide infra). If we

M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
133
The crystal structure of dimer 6 is displayed in Fig. 2.
Although related compound [Au(C6F5)2Cl]2 has been
known for a long time [9] 6 is the only complex of the
type [AuR2X]2 or [AuRX2]2 (with R=aryl) to have
been structurally characterised. However, the crystal
structures of [AuEt2Br]2 [34] and [AuMeBr2]2 [35] were
reported a few decades ago. The molecular structure of
6 is planar and consists of discrete units of two gold
atoms (with mesityl ligands in cis), each in a square-
planar configuration and held by two chlorine atoms.
,
The Au–Cipso distances (2.033(3) and 2.038(3) A) are
shorter than the distances Au–C found for complex 2
and almost identical to those described for
[Au(mes)2(bipy)]ClO4 (7) (vide supra). The bond angles
around the gold atoms in 6 are all close to 90° and lie
between the values of 92.98(8)° for C(10)–Au(1)–Cl(1)
and 84.53(2)° for Cl(1)–Au(1)–Cl(1c) (Table 3).
These values are comparable to those found in
[AuEt2Br]2 [34] and [AuMeBr2]2 [35]. The Au–Cl dis-
Fig. 2. Molecule of compound 6 in the crystal. Displacement para-
meter ellipsoids represent 50% probability surfaces. H atoms are
omitted for clarity.
,
tances of 2.4457(8) and 2.4504(8) A are slightly longer
than observed in 2 as expected for chloro atoms acting
as bridges between metallic centres and being trans to a
mesityl group.
Table 3
a
,
Bond lengths (A) and angles (°) for 6
Bond lengths
Au(1)–C(1)
Au(1)–Cl(1)
Cl(1)–Au(1"1)
C(1)–C(6)
C(2)–C(9)
C(4)–C(5)
2.033(3)
2.4457(8) Au(1)–Cl(1"1)
2.4504(8) C(1)–C(2)
1.394(4)
1.508(4)
1.394(6)
1.384(4)
Au(1)–C(10)
2.038(3)
2.4504(8)
1.394(4)
1.399(4)
1.373(5)
1.522(5)
1.505(5)
3. Experimental
C(2)–C(3)
C(3)–C(4)
C(4)–C(8)
C(6)–C(7)
Instrumentation and general experimental techniques
were as described earlier [11]. Proton and 31P{1H}-
NMR and conductivity data are listed in Table 1. All
the reactions were performed at room temperature (r.t.)
except that of PPN[AuCl4] with Hg(mes)2. Reactions of
1 with silver salts must be carried out avoiding light
exposure until the silver chloride is removed. The start-
ing materials PPN[AuCl2] [36] and [Hg(mes)2] [15] were
prepared as described previously. PPN[AuCl4] was pre-
pared by addition of stoichiometric Cl2 to a solution of
PPN[AuCl2] in dichloromethane. All other reagents
were commercially available. Caution: perchlorate salts
of metal complexes with organic ligands are potentially
explosive. Only small amounts of material should be
prepared and all samples handled with great caution.
C(5)–C(6)
Bond angles
C(1)–Au(1)–C(10)
C(10)–Au(1)–Cl(1)
C(10)–Au(1)–Cl(1"1) 173.15(8) Cl(1)–Au(1)–Cl(1"1) 84.53(2)
Au(1)–Cl(1)–Au(1"1) 95.47(2) C(2)–C(1)–C(6)
C(2)–C(1)–Au(1)
C(1)–C(2)–C(3)
C(3)–C(2)–C(9)
C(5)–C(4)–C(8)
C(5)–C(6)–C(1)
C(1)–C(6)–C(7)
92.73(11) C(1)–Au(1)–Cl(1)
92.98(8) C(1)–Au(1)–Cl(1"1) 90.46(8)
171.63(9)
121.5(3)
122.7(2)
124.5(3)
122.4(3)
122.3(3)
118.8(3)
115.5(2)
117.8(3)
117.7(3)
121.5(4)
118.1(3)
123.1(3)
C(6)–C(1)–Au(1)
C(1)–C(2)–C(9)
C(4)–C(3)–C(2)
C(6)–C(5)–C(4)
C(5)–C(6)–C(7)
a Symmetry transformations used to generate equivalent atoms:
"1: −x+3/2, −y+3/2, −z+1.
3.1. Syntheses
ordination plane of the gold centre in order to minimise
the repulsion between the ortho-methyl groups. The
3.1.1. cis-PPN[Au(mes)2Cl2] (1)
,
Au–Cl distance of 2.381(2) A and the Au–P distances
To PPN[AuCl4] (1.097 g, 1.25 mmol) in acetone (50
ml) was added [Hg(mes)2] (1.369 g, 3.12 mmol). After
heating at reflux for 1.5 h, the yellow mixture became a
yellow solution by solubilisation of the organomercury
reagent. Heating for a further 4.5 h afforded a colour-
less solution. The reaction was usually stopped after 10
h of refluxing (when decomposition to metallic gold
started to be noticed). The solution was cooled and
filtered through Celite. The almost colourless solution
was concentrated in vacuo to ca. 5 ml, and Et2O (20
,
of 2.423(2) A are slightly longer than in other examples
,
of gold(III) complexes with bonds to Cl (e.g. 2.337(8) A
in [Au(C6F5)2Cl(PPh2CH2PPh2)]) [29] or to PPh3 lig-
ands (e.g. 2.389(9) A in [Au(C6F5)2Cl(PPh3)] [30],
2.314(1) A in [Au(S2C6H4)(C6F5)PPh3] [31], 2.335(4) A
,
,
,
,
in [AuCl3(PPh3)] [32] and 2.350(6) and 2.347(6)A (two
independent molecules) in [AuMe3(PPh3)]) [33]. These
elongations of the bonds trans to mesityl inditate the
strong trans influence of this radical.

134
M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
ml) added to precipitate 1 as a white solid. The analyt-
ical sample was purified by recrystallization from
dichloromethane–ether. The Et2O filtrate was concen-
trated in vacuo to ca. 5 ml, and n-hexane (20 ml) added
to afford [Hg(mes)Cl] as a white solid. Compound 1
(1.18 g, 92%): Anal. Found: C, 62.85; H, 5.20; N, 2.53.
Calc. for C54H52N2PCl2Au: C, 63.09; H, 5.10; N, 2.73%.
FAB MS: M−, m/z=505, 100%. IR (cm−1, Nujol): w
(mes)=1588 (w), 855, 845 (m); w (PPN)=1299 (vs, br),
1182, 1161 (m), 1113 (s); w (Au–Cl)=291, 278 (s).
tion of 6 in dichloromethane. Compound 6 (0.048 g,
51%): Anal. Found: C, 46.25; H, 4.40. Calc. for
C36H44Cl2Au2: C, 45.92; H, 4.71%. FAB MS: [M–Au-
(mes)], m/z=384, 11%, [AuCl2]2, m/z=538, 100%. IR
(cm−1, Nujol): w (mes)=1559 (m), 868 (w), 847 (m).
3.1.4. cis-[Au(mes)2(L–L)]X (X=ClO4, L–L=bipy
(7), L–L=phen (8), L–L=dppe (9) X=SO3CF3,
L–L=dppm (10))
To separate solutions of 1 (0.103 g, 0.1 mmol) in
dichloromethane (20 ml) solutions of AgOClO3 (0.042
g, 0.2 mmol) to obtain 7, 8 and 9, or AgOtf (0.051 g,
0.2 mmol) to obtain 10, in diethyl ether (10 ml) were
added. After removal of AgCl and PPN[X] (X=ClO4
or TfO) in the way described in Section 3.1.2, to the
separate filtrates (containing ‘Au(mes)2X’) in diethyl
ether (20 ml) bipy (0.015 g, 0.1 mmol, 7), phen (0.020 g,
0.1 mmol, 8), dppe (0.040 g, 0.1 mmol, 9) or dppm
(0.038 g, 0.1 mmol, 10) were added. All these com-
pounds (7–10) precipitated in the media and were
separated by filtration as white solids. Compound 7
(0.041 g, 60%): Anal. Found: C, 48.15; H, 4.20; N, 4.30.
Calc. for C28H30N2ClO4Au: C, 48.67; H, 4.38; N,
3.1.2. cis-[Au(mes)2ClL] (L=PPh3 (2), P{p-tol}3 (3),
AsPh3 (4), SPPh3 (5))
To separate solutions of 1 (0.209 g, 0.2 mmol) in
dichloromethane (20 ml) solutions of AgOtf (0.051 g,
0.2 mmol) in Et20 (10 ml) were added. AgCl precipi-
tated instantaneously and was removed by filtration of
the reaction mixture through Celite. The resulting
colourless solutions were concentrated in vacuo to ca. 5
ml and addition of Et2O (20 ml) resulted in the precip-
itation of PPN[TfO] which was removed by filtration.
To separate filtrates was added PPh3 (0.047 g, 0.18
mmol), P{p-tol}3 (0.055 g, 0.18 mmol), AsPh3 (0.055 g,
0.18 mmol) or SPPh3 (0.053 g, 0.18 mmol) for the
obtention of 2, 3, 4 and 5, respectively. After stirring at
r.t. for 20 min. the solutions were concentrated in
vacuo to ca. 5 ml and addition of n-hexane (20 ml)
afforded 2–5 as white solids. Crystals of 2 suitable for
an X-ray diffraction study were obtained by slowly
evaporating a solution in dichloromethane. Compound
2 (0.096 g, 73%): Anal. Found: C, 58.45; H, 4.80. Calc.
for C36H37ClPAu: C, 58.98; H, 5.09%. FAB MS: [M–
Cl], m/z=697, 24%. IR (cm−1, Nujol): w (mes)=1586
(w), 855 (s, v br). Compound 3 (0.070 g, 53%): Anal.
Found: C, 60.30; H, 5.60. Calc. for C39H43ClPAu: C,
60.43; H, 5.59%. FAB MS: [M–Cl], m/z=738, 16%.
IR (cm−1, Nujol): w (mes)=1598 (w), 863, 849 (m).
Compound 4 (0.068 g, 49%): Anal. Found: C, 55.80; H,
4.60. Calc. for C36H37AsClAu: C, 55.65; H, 4.80%.
FAB MS: [M–Cl], m/z=741, 20%. IR (cm−1, Nujol):
w (mes)=1582 (m), 855 (s). Compound 5 (0.076 g,
55%): Anal. Found: C, 56.90; H, 4.75; S, 3.80. Calc. for
C36H37ClPSAu: C, 56.51; H, 4.87; S, 4.20%. FAB MS:
[M–Cl], m/z=729, 71%. IR (cm−1, Nujol): w (mes)=
1586 (m), 847 (s).
4.05%. FAB MS: M+, m/z=615, 96%. IR (cm−1
,
Nujol): w (mes)=1588 (m), 849 (m, br); w (ClO4)=1088
(vs, br), 623 (m). Compound 8 (0.032 g, 44%): Anal.
Found: C, 49.90; H, 4.10; N, 3.90. Calc. for
C30H32N2ClO4Au: C, 50.25; H, 4.50; N, 3.90%. FAB
MS: M+, m/z=591, 100%. IR (cm−1, Nujol): w
(mes)=1569 (w), 868, 849 (m); w (ClO4)=1090 (vs, br),
623 (m). Compound 9 (0.066 g, 71%): Anal. Found: C,
56.10; H, 5.20. Calc. for C44H50ClO4P2Au: C, 56.39; H,
5.38%. FAB MS: M+, m/z=832, 39%. IR (cm−1
,
Nujol): w (mes)=1586 (w), 849 (m, br); w (ClO4)=1102
(vs, br), 623 (m). Complex 10 (0.086 g, 88%): Anal.
Found: C, 54.15; H, 4.60; S, 3.25. Calc. for
C44H48F3O3P2SAu: C, 54.32; H, 4.97; N, 3.30%. FAB
MS: M+, m/z=819, 56%. IR (cm−1, Nujol): w (mes)=
1586 (w), 849 (m, br); w (TfO)=1260 (vs, br), 1225 (s),
1156 (s).
3.1.5. cis-[Au(mes)2(L–L)] (L–L=S2CNR2 (R=Me
(11), Et (12), Bz (13)), O2CCF3 (14))
To separate solutions of [Au(mes)2OClO3] (0.1 mmol)
obtained by the procedure described in Section 3.1.4,
solutions of Na[S2CNR2]2H2O (R=Me, 0.018 g, 0.1
mmol, 11; Et, 0.023 g, 0.1 mmol, 12; Bz, 0.029 g, 0.1
mmol, 13) in acetone (10 ml) or [MePPh3]CF3COO
(0.039 g, 0.1 mmol, 14) in dichloromethane (20 ml)
were added. The reaction mixtures were stirred for 40
min (11–13) or 10 min (14) until the dithiocarbamates
or acetate solublised. These slightly yellow solutions
were filtered through celite in order to remove the
QClO4 (Q=Na, 11–13; MePPh3, 14) formed. Concen-
tration of the resulting filtrates to ca. 5 ml and addition
of n-hexane (20 ml) gave 11 and 14 as white and 12 and
3.1.3. cis-[Au(mes)2Cl] (6)
2
To
a solution of 1 (0.209 g, 0.2 mmol) in
dichloromethane (20 ml) a solution of AgOtf (0.051 g,
0.2 mmol) in Et20 (10 ml) was added. The AgCl and
PPN[TfO] formed were removed from the solution as in
Section 3.1.2. The colourless filtrate in diethyl ether was
concentrated in vacuo to ca. 5 ml and addition of
n-hexane (30 ml) afforded 6 as a pale yellow solid.
Crystals of 6 suitable for an X-ray diffraction study
were obtained by slowly layering n-hexane over a solu-

M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
135
3
,
13 as pale yellow solids. Compound 11 (0.026 g, 46%):
Anal. Found: C, 45.10; H, 5.50; N, 2.65; S, 11.30. Calc.
for C21H28NS2Au: C, 45.40; H, 5.08; N, 11.55; S, 2.50%.
FAB MS: M+, m/z=555, 90%. IR (cm−1, Nujol): w
(mes)=1545 (m), 849 (s). Compound 12 (0.024 g, 42%):
Anal. Found: C, 46.90; H, 5.15; N, 2.45; S, 10.30. Calc.
for C23H32NS2Au: C, 47.33; H, 5.53; N, 2.40; S, 10.80%.
FAB MS: M+, m/z=583, 83%. IR (cm−1, Nujol): w
(mes)=1528 (m), 843 (s). Compound 13 (0.037 g, 53%):
Anal. Found: C, 55.60; H, 4.90; N, 1.90; S, 8.75. Calc.
for C33H36NS2Au: C, 56.00; H, 5.13; N, 1.98; S, 9.05%.
FAB MS: M+, m/z=706, 15%. IR (cm−1, Nujol): w
(mes)=1586 (m), 847 (s). Compound 14 (0.030 g, 55%):
Anal. Found: C, 44.15; H, 3.90. Calc. for
C20H22F3O2Au: C, 43.81; H, 4.04%. FAB MS: M+,
m/z=548, 7%. IR (cm−1, Nujol): w (mes)=1590 (m),
843 (s).
U=3480.7(7) A , Z=4, Dcalc=1.797 Mg m−3, u(Mo–
Ka)=0.71073 A, v=8.596 mm−1, F(000)=1808, T=
,
160(2) K.
3.3.2. Data collection and reduction
A yellow prism ca. 0.38×0.30×0.16 mm3 was
mounted in inert oil on a glass fibre. A total of 10 617
intensities were measured on a Siemens SMART CCD
diffractometer, q range for data collection 2.07–28.35°.
Reflections were corrected for absortion by a semi-em-
pirical method (c-scan) [40]. Merging equivalents gave
3958 unique reflections (Rint 0.0340).
3.3.3. Structure solution and refinement
The structure was solved by direct methods and
instruction of SHELXS 96 [41] and subjected to full-ma-
trix least-squares refinement on F2 (program SHELXL 96
[42]).The non-hydrogen atoms were refined with an-
isotropic thermal parameters. All hydrogen atoms were
included in idealised positions. Refinement proceeds to
R=0.0209, wR=0.0499 and goodness of fit on F2
1.028, and R=0.0239, wR=0.0508 for all data. In the
3.2. Crystal structure determination of compound 2
3.2.1. Crystal data
Compound 2: C36H37AuClP, M=733.04, monoclinic,
final Fourier synthesis the electron density fluctuates in
the range 1.385 to −1.0976 e A
,
,
space group P2(1)/n, a=13.216(3) A, b=11.159(2) A,
−3
3
,
.
,
,
c=21.229(3) A, i=104.71(3)°, U=3028.2(10) A ,
Z=4, Dcalc=1.608 Mg m−3, u(Mo–Ka)=0.71069 A,
,
v=5.023 mm−1, F(000)=1456, T=150(2) K.
4. Supplementary material
3.2.2. Data collection and reduction
Crystallographic data for the structural analysis (ex-
cluding structure factors) have been deposited with the
Cambridge Crystallographic Data Centre, CCDC nos.
141725 and 141726. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
A yellow prism ca. 0.16×0.14×0.12 mm3 was
mounted in inert oil on a glass fibre. A total of 10 950
intensities were measured on a Delf Instruments TV
area detector diffractometer, q range for data collection
1.98–25.06°. A Lorentz-polarization type absorption
correction was applied using the program DIFABS [37].
Merging equivalents gave 4566 unique reflections (Rint
0.0751).
3.2.3. Structure solution and refinement
Acknowledgements
The structure was solved by PATT instruction of
SHELXS 86 [38] and subjected to full-matrix least-squares
refinement on F2 (program SHELXL 93 [39]).The non-hy-
drogen atoms were refined with anisotropic thermal
parameters. All hydrogen atoms were included in ide-
alised positions. Refinement proceeds to R=0.0400,
wR=0.092 and goodness of fit on F2 0.922 for 358
parameters and six restraints, and R=0.0566, wR=
0.0924 for all data. In the final Fourier synthesis the
The Spanish authors thank the Direccio´n General de
Ensen˜anza Superior (Grant PB98-0542) for financial
support and M.B.H. thanks the Engineering and Physi-
cal Sciences Research Council for support of the X-ray
facilities.
References
electron density fluctuates in the range 2.619 to −1.330
−3
,
e A
.
[1] H. Schmidbaur, A. Grohmann, M.E. Olmos, Gold: Progress in
Chemistry, Biochemistry and Technology, Wiley, Chichester,
1999, p. 710.
[2] R. Uso´n, A. Laguna, Coord. Chem. Rev. 70 (1986) 1.
[3] A. Laguna, M.C. Gimeno, Trends Organomet. Chem. 1 (1994)
231.
[4] R.J. Puddephatt, in: G. Wilkinson, F.G.A. Stone, E.W. Abel
(Eds.), Comprehensive Organometallic Chemistry, vol. 2, 1st
edn, Pergamon Press, Oxford, 1982, p. 765.
3.3. Crystal structure determination of compound 6
3.3.1. Crystal data
Compound 2: C36H44Au2Cl2, M=941.55, mono-
clinic, space group C2/c, a=21.432(2) A, b=
,
,
,
9.8423(11) A, c=16.942(2) A, i=103.094(3)°,

136
M. Contel et al. / Journal of Organometallic Chemistry 607 (2000) 129–136
[5] M. Paul, H. Schmidbaur, Z. Naturforsch. 496 (1994)
647.
[24] P.A. Bonnardel, R.V. Parish, R.G. Pritchard, J. Chem. Soc.
Dalton Trans. (1996) 3185.
[25] M.N. Gowda, S.B. Waikar, G.K.N. Reddy, Adv. Inorg. Chem.
Radiochem. 28 (1984) 255.
[6] R. Uso´n, A. Laguna, M. Laguna, E. Fernandez, Inorg. Chim.
Acta 45 (1980) L177.
[26] D.H. Johnston, D.F. Shriver, Inorg. Chem. 32 (1993) 1045.
[27] P.E. Garrou, Chem. Rev. 81 (1981) 229.
[28] R. Uso´n, A. Laguna, E.J. Ferna´ndez, M.E. Ruiz, P.G. Jones, J.
Lautner, J. Chem. Soc. Dalton Trans. (1989) 2127.
[29] R. Uso´n, A. Laguna, M. Laguna, B.R. Manzano, P.G. Jones,
G.M. Sheldrick, J. Chem. Soc. Dalton Trans. (1985) 2417.
[30] R.W. Baker, P. Pauling, J. Chem. Soc. D. (1969) 745.
[31] E. Cerrada, E.J. Fernandez, M.C. Gimeno, A. Laguna, M.
Laguna, R. Terroba, M.D. Villacampa, J. Organomet. Chem.
492 (1995) 105.
[32] G. Bandoli, D.A. Clemente, G. Marangoni, L. Cattalini, J.
Chem. Soc. Dalton Trans. (1973) 886.
[33] J. Stein, J.P. Fackler Jr, C. Paparizos, H.W. Chen, J. Am. Chem.
Soc. 103 (1981) 2192.
[34] A. Burawoy, C.S. Gibson, G.C. Hampson, H.M. Powell, J.
Chem. Soc. (1937) 1690.
[35] S. Komiya, J.C. Huffman, J.K. Kochi, Inorg. Chem. 16 (1977)
1253.
[36] P. Braunstein, R.J.H. Clark. J. Chem. Soc. Dalton Trans. (1973)
1845.
[37] N.P.C. Walker, D. Stuart, Acta Crystallogr. Sect. A 39 (1983)
158 (adapted for FAST geometry by A. Karaulov, University of
Wales, Cardiff, 1991).
[38] G.M. Sheldrick, SHELXS 86, Acta Crystallogr. Sect. A 46 (1990)
467.
[39] G.M. Sheldrick, SHELXL 93, Program for Crystal Structure
Refinement, University of Go¨ttingen, Go¨ttingen, Germany,
1993.
[40] A.C.T. North, D.C. Phillips, F.S. Mathews, Acta Crystallogr.
Sect. A 24 (1968) 351.
[41] G.M. Sheldrick, SHELXS-96, Siemens Analytical X-ray Instru-
ments, Madison, WI, 1990.
[42] G.M. Sheldrick, SHELXL-96, Program for Crystal Structure
Refinement, University of Go¨ttingen, Go¨ttingen, Germany,
1996.
[7] J. Vicente, M.T. Chicote, A. Arcas, M. Artigao, Inorg. Chim.
Acta 65 (1982) L251.
[8] J. Vicente, M.T. Chicote, A. Arcas, M. Artigao, R. Jime´nez, J.
Organomet. Chem. 247 (1983) 123.
[9] R. Uso´n, A. Laguna, M. Laguna, M. Abad, J. Organomet.
Chem. 249 (1983) 437.
[10] R. Uso´n, A. Laguna, J. Garcia, M. Laguna, Inorg. Chim. Acta
37 (1979) 201.
[11] M. Contel, J. Jime´nez, P.G. Jones, A. Laguna, M. Laguna, J.
Chem. Soc. Dalton Trans. (1994) 2515.
[12] M. Contel, J. Garrido, M.C. Gimeno, P.G. Jones, A. Laguna,
M. Laguna, Organometallics 15 (1996) 4939.
[13] M. Contel, J. Garrido, M.C. Gimeno, J. Jime´nez, P.G. Jones, A.
Laguna, M. Laguna, Inorg. Chim. Acta 254 (1997) 157.
[14] V.W-W. Yam, S.W.-K. Choi, T.-F. Lai, W.-K. Lee, J. Chem.
Soc. Dalton Trans. (1993) 1001.
[15] M. Laguna, M.D. Villacampa, M. Contel, J. Garrido, Inorg.
Chem. 37 (1998) 133.
[16] J. Vicente, M.T. Chicote, M.D. Bermu´dez, Inorg. Chim. Acta 63
(1982) 35.
[17] J. Vicente, M.T. Chicote, M.D. Bermu´dez, J. Organomet. Chem.
268 (1984) 191.
[18] J. Vicente, M.T. Chicote, M.D. Bermu´dez, X. Sola´ns, M. Font-
Altaba, J. Chem. Soc. Dalton Trans. (1984) 557.
[19] J. Vicente, M.D. Bermu´dez, M.J. Sa´nchez-Santano, J. Paya´,
Inorg. Chim. Acta 174 (1990) 53.
[20] J. Vicente, M.D. Bermu´dez, J. Escribano, M.P. Carrillo, P.G.
Jones, J. Chem. Soc. Dalton Trans. (1990) 3083.
[21] J. Vicente, M.D. Bermu´dez, J. Escribano, Organometallics 10
(1991) 3380.
[22] E.C. Constable, T.A. Leese, J. Organomet. Chem. 363 (1989)
419.
[23] P.A. Bonnardel, R.V. Parish, J. Organomet. Chem. 515 (1996)
221.
.