Synthesis of 2,4,6-tris(trifluoromethyl)phenyl complexes of gold and thallium

Article abstract of DOI:10.1016/S0022-328X(01)01390-0

Reaction of [AuCl(AsPh₃)] with [LiFmes] (Fmes = 2,4,6-tris(trifluoromethyl)phenyl) leads to the gold(I) complex [Au(Fmes)(AsPh₃)], which can be used as precursor to other gold(I) complexes by displacement of AsPh₃. Thus, treatment with diphosphines leads to mono- or dinuclear gold(I) complexes, namely [Au(Fmes)(dppm)], [Au(dppe)₂][Au(Fmes)₂] or [{Au(Fmes)}₂(μ-P-P)] (P-P: bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe)). X-ray diffraction studies of [{Au(Fmes)}₂(μ-P-P)] show the expected trans-conformation for dppe but an unexpected gauche conformation for the dppm derivative. There are no short gold-gold contacts. The ionic nature of [Au(dppe)₂][Au(Fmes)₂] was also established by X-ray methods. Reaction of TlCl₃ with [LiFmes] affords [Tl(Fmes)₃], which does not react further with gold(I) derivatives to give gold(III) derivatives.

Full text of DOI:10.1016/S0022-328X(01)01390-0

Journal of Organometallic Chemistry 648 (2002) 1–7
www.elsevier.com/locate/jorganchem
Synthesis of 2,4,6-tris(trifluoromethyl)phenyl complexes of gold
and thallium
Manuel Bardaj´ı a, Peter G. Jones b, Antonio Laguna a,*, Ana Moracho a,
Axel K. Fischer c
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC,
E-50009, Zaragoza, Spain
b Institut fu¨r Anorganische und Analytische Chemie der Technischen Uni6ersita¨t, Postfach 3329, D-38023 Braunschweig, Germany
c Institut fu¨r Chemie, Uni6ersita¨t Magdeburg, Uni6ersita¨tsplatz 2, D-39106 Magdeburg, Germany
Received 11 December 2000; accepted 19 October 2001
Abstract
Reaction of [AuCl(AsPh3)] with [LiFmes] (Fmes=2,4,6-tris(trifluoromethyl)phenyl) leads to the gold(I) complex
[Au(Fmes)(AsPh3)], which can be used as precursor to other gold(I) complexes by displacement of AsPh3. Thus, treatment with
diphosphines leads to mono- or dinuclear gold(I) complexes, namely [Au(Fmes)(dppm)], [Au(dppe)2][Au(Fmes)2] or
[{Au(Fmes)}2(m-PꢀP)] (PꢀP: bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe)). X-ray diffraction
studies of [{Au(Fmes)}2(m-PꢀP)] show the expected trans-conformation for dppe but an unexpected gauche conformation for the
dppm derivative. There are no short gold–gold contacts. The ionic nature of [Au(dppe)2][Au(Fmes)2] was also established by
X-ray methods. Reaction of TlCl3 with [LiFmes] affords [Tl(Fmes)3], which does not react further with gold(I) derivatives to give
gold(III) derivatives. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Gold; Thallium; Diphosphine; Fluoroaryl
complexes of main group elements or transition metals
with low oxidation states or low coordination numbers
[2]. Recently, Espinet et al. have described some gold(I)
and gold(III) derivatives of Fmes [3].
In this paper we report the synthesis and structural
characterisation of some gold and thallium complexes
with the tris(trifluoromethyl)phenyl ligand. We have
also determined the crystal structure of the gold(I)
complexes [Au(dppe)2][Au(Fmes)2], {Au(Fmes)}2(m-
dppm) and {Au(Fmes)}2(m-dppe).
1. Introduction
The organometallic chemistry of gold has been devel-
oped with two principal types of ligand: ylides or
pentafluorophenyl groups [1]. Both kinds of complexes
are much more stable than the corresponding deriva-
tives with conventional alkyl or aryl ligands. The higher
stability of pentafluorophenyl derivatives has been at-
tributed to two factors: (a) the high electronegativity of
the ligand, which can produce some ionic character in
the goldꢀcarbon bond and some p back-donation from
gold to carbon; and (b) the relative bulkiness of the
ligand. The 2,4,6-tris(trifluoromethyl)phenyl ligand
(Fmes) is a closely related ligand that is less electroneg-
ative (although still highly electron-withdrawing) but
has a higher steric demand than the pentafluorophenyl
group. These properties have been exploited to stabilise
2. Results and discussion
2.1. Synthesis and characterisation
The reaction of lithium 2,4,6-tris(trifluoromethyl)-
phenyl, prepared in situ, with [AuCl(AsPh3)] (molar
ratio 2:1) leads to the gold(I) complex [Au(Fmes)-
(AsPh3)] (1). This derivative is a precursor to other
tris(trifluoromethyl)phenylgold(I) complexes, by dis-
* Corresponding author. Tel.: +34-976-761185; fax: +34-976-
761187.
E-mail address: alaguna@posta.unizar.es (A. Laguna).
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01390-0

2
M. Bardaj´ı et al. / Journal of Organometallic Chemistry 648 (2002) 1–7
placement of the triphenylarsine ligand (Scheme 1).
Complex 1 reacts with diphosphines in a 1:1 molar
ratio to give gold(I) derivatives [Au(Fmes)(dppm)] (2)
or [Au(dppe)2][Au(Fmes)2] (3). The latter has been pre-
pared as the tetraalkylammonium salt in [3]. We were
not able to isolate complex 2 as a solid and we there-
fore, describe only its spectroscopic data. Complex 2 is
highly soluble in hexane and an oily solid is obtained
even at low temperature; this derivative can be pre-
pared from the precursor [Au(Fmes)(tht)] (described in
Ref. [3]) but again an oily solid was obtained. The
reaction of complex 1 with diphosphines in a 2:1 molar
ratio affords the dinuclear gold(I) derivatives 4–5,
which can be also synthesised by addition of complex 1
to an in situ solution of complexes 2–3. These deriva-
tives are air- and moisture-stable white solids at room
temperature.
spectra show the pattern arising from one Fmes group,
a singlet at ca. −60 ppm for the ortho-CF3 and
another at ca. −63 ppm for the para-CF3. The
31P{1H}-NMR spectra of complexes 4 and 5 show a
singlet at 31.6 and 40.2 ppm, respectively. The 31P{1H}-
NMR spectrum of complex 2 shows two broad reso-
nances at 32 and −22 ppm, which at −55 °C are seen
as doublets. The values of the chemical shifts and the
presence of PꢀP coupling imply that the diphosphine
dppm is monocoordinated to one Au(Fmes) unit, with
its second phosphine ‘arm’ free, at least at low temper-
ature. The 31P{1H}-NMR spectrum of complex 3 shows
only one signal, at ca. 15 ppm. The LSIMS mass
spectra show the peaks corresponding to [M-Fmes]+ at
m/z (% abundance)=503(100), 581(60), 1059(100),
1073(60), for 1, 2, 4, and 5 respectively; in the LSIMS
mass spectrum of complex 3, the peak from the cation
[Au(dppe)2]+ is observed at 993(65%).
The 1H-NMR spectra show the Fmes protons as
singlets at ca. 8 ppm, and also signals from the
triphenylarsine or diphosphine ligands. The 19F-NMR
In order to obtain dinuclear gold(I)–gold(III) com-
plexes containing both pentafluorophenyl and Fmes
Scheme 1.
Scheme 2.

M. Bardaj´ı et al. / Journal of Organometallic Chemistry 648 (2002) 1–7
3
Treatment of TlCl3 with a freshly prepared [LiFmes]
solution (molar ratio 1:4) affords complex 7 [Tl(Fmes)3]
as a white solid, the first thallium complex containing
this ligand. The IR spectrum does not show any TlꢀCl
absorption. A unique type of Fmes ligand is seen in the
1H- and 19F-NMR spectra, and all the resonances are
strongly coupled to thallium, as reported for pen-
tafluorophenylthallium derivatives [5] but in contrast to
thallium 2,4,6-tris(trifluoromethyl)phenoxide, where no
TlꢀH or TlꢀF couplings were reported [6]. The parent
peak of the LSIMS mass spectrum corresponds to
[M−Fmes]+ at 767. To obtain gold(III) complexes by
aryl oxidative transfer from thallium to gold, a well-
known method with [TlCl(C6F5)2], or at least to trans-
fer Fmes to gold [7], we proceeded to treat derivative 7
with [Au(C6F5)(tht)], but there was no reaction after
several days; under refluxing conditions, the gold(I)
complex decomposed without reaction.
Fig. 1. Molecular structure of complex 3 showing the atom-number-
ing scheme. All H atoms have been omitted for clarity.
Table 1
,
Selected bond lengths (A) and angles (°) for complex 3
Bond lengths
Au(1)ꢀP(2)
Au(1)ꢀP(3)
Au(1)ꢀP(1)
Au(1)ꢀP(4)
2.3908(6)
2.3941(7)
2.4038(6)
2.4092(6)
C(1)ꢀC(2)
C(3)ꢀC(4)
Au(2)ꢀC(101)
Au(2)ꢀC(91)
1.529(3)
1.538(4)
2.054(2)
2.065(2)
2.2. Crystal structures
In order to determine the molecular structure of
complex 3, we have carried out an X-ray diffraction
analysis. Complex 3 is an ionic complex, namely [Au-
(dppe)2][Au(Fmes)2], as shown in Fig. 1, with selected
bonds and angles in Table 1. The synthesis and struc-
ture of the tetrabutylammonium salt of the same anion
was recently described by some of us [3]. The structure
of the anion in 3 is with one exception closely similar to
that in Ref. [3] (where a more detailed discussion will be
found), with a CꢀAuꢀC angle of 179.58(9)°, AuꢀC
Bond angles
P(2)ꢀAu(1)ꢀP(3) 126.63(2)
P(2)ꢀAu(1)ꢀP(1) 86.38(2)
P(3)ꢀAu(1)ꢀP(1) 117.33(2)
P(2)ꢀAu(1)ꢀP(4) 120.43(2)
P(3)ꢀAu(1)ꢀP(4)
P(1)ꢀAu(1)ꢀP(4)
C(101)ꢀAu(2)ꢀC(91) 179.58(9)
85.70(2)
125.06(2)
,
bond lengths of 2.054(2) and 2.065(2) A, and narrow
ring angles at the ipso C atoms (113.9, 113.3(2)°; this is
a common feature of aryl complexes of coinage and
related metals [3]). Similar values are observed in
derivatives 4 and 5 (see below). The exception concerns
the angle between the two aryl ligand planes, which is
27° in Ref. [3] but only 19° in 3.
Various salts of the cation have previously been
subjected to crystal structure determination, seeking
structure relationships with their reported antitumour
activity in mice [8,9]. The gold centre is tetracoordi-
nated with almost equal AuꢀP bond lengths of
Fig. 2. Molecular structure of complex 4 showing the atom-number-
ing scheme. All H atoms have been omitted for clarity.
ligands, the reaction of complex 2 with [Au(C6F5)3(tht)]
has been carried out (Scheme 2). The process however
leads to a mixture of three dinuclear complexes: the
expected mixed derivative 6 accompanied by two sym-
metrical complexes containing two Au(Fmes) or two
Au(C6F5)3 units (in a 3.4:1:1 molar ratio), as shown by
the NMR spectra (Section 3).
The reaction of complex 2 with silver perchlorate (in
the molar ratio 2:1) leads to a mixture which mainly
contains complex 4 and [Ag2(OClO3)2(dppm)3], instead
of gold(I)–silver(I) complexes as described for the simi-
lar derivative [Au(mesityl)(dppm)] (mesityl=2,4,6-tris(-
methyl)phenyl) [4].
,
2.3908(6)–2.4092(6) A, similar to those reported in
[Au(dppe)2]Cl [10] and [Au(dppe)2][SbF6] [11]. The
PꢀAuꢀP angles are 85.70(2) and 86.38(2)° for the bite
angles and 117.33(2)–126.63(2)° for the others, cf. [Au-
(dppe)2]Cl 85.4(1)–129.6(1)° and [Au(dppe)2][SbF6]
86.4(1)–130.6(1)°.
X-ray diffraction studies of complexes 4 and 5 were
carried out to determine whether the bulkiness of the
ligand affects the geometry of the molecule compared
to other less hindered complexes. Fig. 2 shows the
molecule of 4, with selected bond lengths and angles in
Table 2; it displays crystallographic twofold symmetry.
The gold(I) centre displays an almost linear coordina-

4
M. Bardaj´ı et al. / Journal of Organometallic Chemistry 648 (2002) 1–7
,
,
3.251(1) A in [(AuMe)2(m-dppm)] [12], 3.3307(9) A in
tion, with a CꢀAuꢀP angle of 174.56(10)°. The ring
angle at the ipso carbon is narrow, 114.8(3)°. There are
no short gold–gold contacts, the intramolecular AuꢀAu
t
,
[(AuCC Bu)2(m-dppm)] [13], 3.236(1) A in [{Au(SeC-
,
(NH2)2)}2(m-dppm)]Cl2 [14], 3.1680(3) A in [(AuSiPh3)2-
(m-dppm)] [15], and 3.163(1) A in [{Au(C6F5)}2(m-
,
,
distance being 7.041 A and the shortest intermolecular
dppm)] which also contains a fluorophenyl ligand [16].
Curiously the dinuclear gold(III) complex with a bridg-
ing dppm and 2,6-diphenylpyridine acting as tridentate
C,N,C-donor ligand also shows a cis geometry, al-
though in this case the p stacking of these ligands,
which prefer to be parallel to each other, can favour
this conformation [17]. An intermediate case is pre-
sented by the complex [(AuCl)2(m-dppm)], which shows
,
more than 6.6 A. The latter goldꢀgold distance can be
rationalised in terms of the steric bulk of the Fmes
ligand, which does not allow a cis conformation of the
diphosphine; the observed torsion angle AuꢀP···P%ꢀAu%
is −109° (gauche). This contrasts with other cases
containing a single dppm bridge, where a cis conforma-
tion is preferred, leading to short goldꢀgold distances
,
such as the 3.154(1) A found in [(AuPh)2(m-dppm)] [12],
,
a goldꢀgold distance of 3.341(1) A with a PAu···AuP
torsion angle of 68° [18].
Table 2
,
The AuꢀP distance of 2.2844(9) A is slightly longer
,
Selected bond lengths (A) and angles (°) for complex 4
than those reported in [(AuCCtBu)2(m-dppm)] (2.266(2)
Bond lengths
,
and 2.268(2) A) but appreciably shorter than in
AuꢀC(11)
AuꢀP(1)
P(1)ꢀC(31)
2.069(3)
2.2844(9)
1.821(4)
P(1)ꢀC(21)
P(1)ꢀC(1)
1.835(4)
1.843(3)
,
[(AuSiPh3)2(m-dppm)] (2.357(1) and 2.370(1) A). The
AuꢀP distance and the AuꢀC distance (2.069(3) A) are
similar to those in alkyl or aryl derivatives with a dppm
bridge.
The crystal structure of complex 5 is shown in Fig. 3,
with selected bond lengths and angles in Table 3. It
displays inversion symmetry about the mid-point of the
ethane CꢀC bond. The geometry around the gold atom
is linear, CꢀAuꢀP 178.69(6)°, and the angle at the ipso
C of Fmes is narrow at 115.0(2)°. The long intramolec-
,
Bond angles
C(11)ꢀAuꢀP(1)
C(31)ꢀP(1)ꢀC(21) 105.73(17) C(21)ꢀP(1)ꢀAu
C(31)ꢀP(1)ꢀC(1) 103.15(18) C(1)ꢀP(1)ꢀAu
174.56(10) C(31)ꢀP(1)ꢀAu
112.80(12)
116.09(13)
111.85(8)
C(21)ꢀP(1)ꢀC(1) 106.16(14) P(1)c1ꢀC(1)ꢀP(1) 116.2
Symmetry transformation used to generate equivalent atoms: c1,
−x+1, y, −z+1/2.
,
ular goldꢀgold distance (5.092 A) is associated with the
symmetry-imposed trans conformation of dppe, which
is the commonest in complexes containing a single dppe
bridge, as found in [(AuS2CNEt2)2(m-dppe)] [19],
[(AuCl)2(m-dppe)] [20], [(AuSePh)2(m-dppe)] [21], [(AuS-
carborane)2(m-dppe)] (S-carborane is 1,2-dicarba-closo-
dodecaborane-1-thiolate) [22], [{Au(Si(SiMe3)3)}2(m-
dppe)] [15] and the related derivative [(AuMes)2(m-
dppe)] (Mes=2,4,6-tris(methyl)phenyl) [23]. To the
best of our knowledge, the cis-conformation has only
been reported in [(AuCCPh)2(m-dppe)] (AuꢀAu distance
,
of 3.153(2) A) [24] and in a dinuclear gold(III) complex
containing a dppe bridge and 2,6-diphenylpyridine act-
ing as tridentate C,C,N-donor ligand, although as in
the dppm derivate (see above) the p stacking of these
ligands favours this conformation [17]. The shortest
Fig. 3. Molecular structure of complex 5 showing the atom-number-
ing scheme. All H atoms have been omitted for clarity.
Table 3
,
intermolecular AuꢀAu distance is more than 8 A, in
,
Bond lengths (A) and angles (°) for complex 5
,
contrast to 3.0442(9) A in [(AuSePh)2(m-dppe)] (form-
,
ing polymeric chains) and 3.189(1) A in [(AuCl)2(m-
Bond lengths
dppe)] (forming dimers). The AuꢀP and the AuꢀC bond
AuꢀC(1)
AuꢀP
PꢀC(21)
2.064(2)
2.2804(6)
1.813(2)
PꢀC(10)
PꢀC(11)
1.831(2)
1.813(2)
,
lengths, 2.2804(6) and 2.064(2) A respectively, are simi-
lar to those found in complex 4 and in [(AuMes)2(m-
dppe)].
Bond angles
C(1)ꢀAuꢀP
C(21)ꢀPꢀC(11)
C(10)ꢀPꢀAu
C(21)ꢀPꢀC(10)
178.69(6)
108.02(9)
113.14(7)
104.14(9)
C(11)ꢀPꢀC(10)
C(21)ꢀPꢀAu
C(11)ꢀPꢀAu
104.99(9)
113.68(7)
112.18(7)
In conclusion, we describe the synthesis of the first
Fmes thallium complex and a new Fmes gold(I) precur-
sor, from which fluoromesityl–phosphino–gold(I) com-
plexes can be prepared. The high steric demand of this
ligand leads to an unusual gauche-conformation in the
dinuclear diphosphine complex {Au(Fmes)}2(m-PPh2-
Symmetry transformations used to generate equivalent atoms: c1:
−x+2, −y+1, −z+1.

M. Bardaj´ı et al. / Journal of Organometallic Chemistry 648 (2002) 1–7
5
CH2PPh2). We have shown that mononuclear com-
plexes of the same stoichiometry [Au(Fmes)(PꢀP)] have
different molecular structure depending on the diphos-
phine, [Au(Fmes)(dppm)] and [Au(dppe)2][Au(Fmes)2].
581 (60, [Au(dppm)]+), 862 (50, [M]+), 965 (20, [Au-
(dppm)2]+), 1059 (100, [Au2(Fmes)(dppm)]+).
3.4. Preparation of [Au(dppe)2][Au(Fmes)2] (3)
To a CH2Cl2 solution (10 ml) of 1 (0.1 mmol, 78 mg)
was added the diphosphine dppe (0.1 mmol, 40 mg).
After stirring for 30 min, the solution was evaporated
to ca. 1 ml. Addition of petroleum ether afforded
complex 3 as a white solid. Yield of 3: 48 mg, 55%.
1H-NMR: l 8.14 (s, 2H, Fmes), 7.6–7.4 (m, 20H, Ph),
2.47 (s, 4H, CH2ꢀP). 19F-NMR: l −60.42 (s, 6Fo),
−63.47 (s, 3Fp). 31P{1H}-NMR: l 15.1 (br). Anal.
Calc. for C70H52Au2F18P4: C, 47.95; H, 3.0. Found: C,
47.7; H, 2.75%. LSIMS (m/z, %, assignment): 595 (100,
[Au(dppe)]+), 876 (90, [Au(Fmes)(dppe)]+), 993 (65,
[Au(dppe)2]+), 1073 (15, [Au2(Fmes)(dppe)]+).
3. Experimental
3.1. General
All the reactions were carried out under an argon
atmosphere at room temperature (r.t.). 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-, 19F- and 31P{1H}-
NMR spectra were recorded on a Bruker ARX 300 or
GEMINI 2000 apparatus in CDCl3 solutions (if no
other solvent is stated); chemical shifts are quoted
relative to SiMe4 (external, H), CFCl3 (external, 19F)
3.5. Preparation of [{Au(Fmes)}2(v-PꢀP)];
PꢀP=dppm (4), dppe (5)
1
and 85% H3PO4 (external, 31P). C, H, N and S analyses
were performed with a Perkin–Elmer 2400 microanaly-
ser. Mass spectra were recorded on a VG Autospec
using LSIMS technique (with Cs gun) and 3-nitroben-
zyl alcohol as matrix. Caution: thallium compounds are
highly toxic and must be handled with special care.
These complexes can be prepared in two different
ways: (a) To a 10 ml Et2O solution of 1 (0.1 mmol, 78
mg) was added the diphosphine (0.05 mmol; dppm 19
mg, dppe 20 mg). After stirring for 1 h, the solution
was concentrated to ca. 1 ml. Addition of petroleum
ether afforded complexes 4–5 as white solids. (b) To a
5 ml Et2O (or 1 ml CDCl3) solution of 2 (0.05 mmol) or
3 (0.025 mmol; 44 mg) was added the corresponding
amount of complex 1 (0.05 mmol; 39 mg). Then as
3.2. Preparation of [Au(Fmes)(AsPh3)] (1)
To a freshly prepared Et2O solution of Li(Fmes)
(Fmes=1,3,5-tris(trifluoromethyl)phenyl; 0.6 mmol)
[25] was added [AuCl(AsPh3)] (0.162 g, 0.3 mmol) [26].
After stirring for 6 h, two drops of water were added to
hydrolyse the excess of lithium derivative. The mixture
was evaporated to dryness, then CH2Cl2 was added and
the solution filtered through a Na2SO4 sinter. The clear
solution was evaporated to ca. 1 ml, and addition of
petroleum ether afforded 1 as a white solid. Yield of 1:
1
stated in (a). Yield of 4: 40 mg, 60%. H-NMR: l 7.88
2
(s, 4H, Fmes), 7.6–7.3 (m, 20H, Ph), 3.63 (t, J(HP)=
10.2 Hz, 2H, CH2ꢀP). 19F-NMR: l −60.60 (s, 6Fo),
−63.66 (s, 3Fp). 31P{1H}-NMR: l 31.6 (s). Anal. Calc.
for C43H26Au2F18P2: C, 38.55; H, 1.95. Found: C,
38.25; H, 1.85. LSIMS (m/z, %, assignment): 581 (20,
[Au(dppm)]+), 1059 (100, [Au2(Fmes)(dppm)]+). Yield
of 5: 45 mg, 66%. 1H-NMR: l 8.10 (s, 4H, Fmes),
7.7–7.2 (m, 20H, Ph), 2.79 (s, 4H, CH2ꢀP); 19F-NMR:
l −60.09 (s, 6Fo), −63.24 (s, 3Fp). 31P{1H}-NMR: l
40.2 (s). Anal. Calc. for C44H28Au2F18P2: C, 39.0; H,
2.08. Found: C, 39.35; H, 2.4%. LSIMS (m/z, %,
assignment): 595 (100, [Au(dppe)]+), 1073 (60,
[Au2(Fmes)(dppe)]+).
1
155 mg, 66%. H-NMR: l 8.08 (s, 2H, Fmes), 7.6–7.3
(m, 15H, Ph). 19F-NMR: l −60.9 (s, 6Fo), −63.51 (s,
3Fp). Anal. Calc. for C27H17AuAsF9: C, 41.35; H, 2.2.
Found: C, 41.2; H, 2.0%. LSIMS (m/z, %, assignment):
503 (100, [M−(Fmes)]+), 809 (45, [Au(AsPh3)2]+).
3.3. Preparation of [Au(Fmes)(dppm)] (2)
To a deuterated CHCl3 solution (1 ml) or CH2Cl2
3.6. Reaction of [Au(Fmes)(dppm)] with [Au(C6F5)3(tht)]
solution (10 ml) of
1 (0.1 mmol, 78 mg) or
[Au(Fmes)(tht)] (0.1 mmol, 57 mg) was added the
diphosphine dppm (0.1 mmol, 38 mg). After stirring for
30 min, derivative 2 is formed, as seen in the NMR
To a 10 ml Et2O (or 1 ml CDCl3) solution of 2 (0.05
mmol) was added [Au(C6F5)3(tht)] (0.05 mmol; 39 mg)
[27]. After stirring for 1 h, the solution was concen-
trated to ca. 1 ml. Addition of petroleum ether afforded
a mixture of complexes [(Fmes)Au(m-dppm)Au(C6F5)3]
(6), [{Au(Fmes)}2(m-dppm)] (4) and [{Au(C6F5)3}2(m-
dppm)] as white solids. NMR data for complex 6:
1H-NMR: l 8.01 (s, 2H, Fmes), 7.6–7.3 (m, 20H, Ph),
3.42 (t, 2J(HP)=9.1 Hz, 2H, CH2ꢀP). 19F-NMR: l
1
spectra. NMR data for complex 2. H-NMR: l 8.05 (s,
2H, Fmes), 7.6–7.3 (m, 20H, Ph), 3.16 (br, 2H,
CH2ꢀP). 19F-NMR: l −60.57 (s, 6Fo), −63.44 (s,
3Fp). 31P{1H}-NMR: l 32.0 (br, 1P), −22.1 (br, 1P);
31P{1H}-NMR (−55 °C): l 32.0 (d, 2J(PP)=105.9
Hz, 1P), −22.1 (d, 1P). LSIMS (m/z, %, assignment):

6
M. Bardaj´ı et al. / Journal of Organometallic Chemistry 648 (2002) 1–7
Table 4
Details of crystal data and structure refinement for complexes 3, 4 and 5
Compound
3
4
5
Empirical formula
Formula weight
Temperature (K)
C70H52Au2F18P4
1752.93
143(2)
C
43H26Au2F18P2
C44H28Au2F18P2
1354.54
143(2)
1340.51
173(2)
,
Wavelength (A)
0.71073
Triclinic
0.71073
Monoclinic
C2/c
21.2598(6)
8.6920(2)
24.9461(6)
90
114.704(3)
90
4187.90(18)
4
2.126
7.188
0.71073
Monoclinic
P21/c
11.4503(14)
9.3155(10)
20.643(2)
90
96.279(3)
90
2188.6(4)
Crystal system
Space group
(
P1
,
a (A)
12.038(2)
,
b (A)
13.803(2)
20.239(4)
92.257(6)
99.150(6)
99.978(6)
3262.3(10)
2
1.785
4.684
1704
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Z
2
Dcalc (Mg m−3
)
2.055
6.878
1284
Absorption coefficient (mm−1
F(000)
)
2536
Crystal habit
Crystal size (mm)
Diffractometer
Theta range for data collection (°)
Index ranges
Colourless tablet
0.29×0.24×0.16
Bruker SMART 1000 CCD
1.02–30.03
−165h516, −195k519,
−285l528
60970
18 974 [Rint=0.0413]
0.862 and 0.670
18974/220/847
0.963
Colourless prism, cut
0.7×0.4×0.3
Siemens SMART CCD
1.80–28.27
−285h522, −115k511,
−235l533
13649
5146 [Rint=0.0306]
0.928 and 0.428
5146/69/294
1.052
Colourless wedge
0.27×0.14×0.10
Bruker SMART 1000 CCD
1.79–30.00
−155h516, −135k513,
−295l529
25278
6368 [Rint=0.0265]
0.945 and 0.600
6368/249/298
1.012
Reflections collected
Independent reflections
Max/min transmission
Data/restraints/parameters
Goodness-of-fit on F2
R1 [I\2|(I)]
0.0230
0.0304
0.0181
wR2 (all data)
0.0490
0.0736
0.0444
Largest difference peak and hole
1.023 and −0.974
1.869 and −2.801
0.908 and −0.989
−3
,
(e A
)
−60.50 (s, 6Fo, CF3), −63.64 (s, 3Fp, CF3), −120.68
(m, 4Fo, C6F5), −122.75 (m, 2Fo, C6F5), −156.79 (t,
1Fp, C6F5), −157.94 (m, 2Fp, C6F5), −160.95 (m, 2Fm,
C6F5), −161.88 (m, 4Fm, C6F5). 31P{1H}-NMR: l
28.0 (d, J(PP)=17.7 Hz, 1P, trans to Fmes), 10.7 (m,
1P).
3.8. Crystal structure determination of complexes 3, 4
and 5
Colourless crystals were obtained from slow diffusion
of petroleum ether 40–60 into a CH2Cl2 solution of the
appropriate complex. Crystal data and details of data
collection and structure refinement are given in Table 4.
Data were measured on SMART area detectors. Absorp-
tion corrections were based on multiple scans (program
SADABS). The structures were refined anisotropically on
F2 (program SHELXL-97 [28]) using a system of re-
straints (to light atom U values and local ring symme-
try). H atoms were included using a riding model.
2
3.7. Preparation of [Tl(Fmes)3] (7)
To a freshly prepared Et2O solution of [Li(Fmes)]
(Fmes=1,3,5-tris(trifluoromethyl)phenyl; 1.6 mmol)
was added TlCl3 (125 mg, 0.4 mmol). After stirring
overnight, two drops of water were added to hydrolyse
the excess of lithium derivative. The mixture was dried
to dryness, then CH2Cl2 was added and filtered through
a Na2SO4 sinter. The clear solution was evaporated to
ca. 1 ml and the addition of petroleum ether afforded 7
4. Supplementary material
1
as a white solid. Yield of 7: 168 mg, 40%. H-NMR: l
Complete X-ray data (excluding structure factors) for
complexes 3, 4 and 5 have been deposited with the
Cambridge Crystallographic Data Centre as supple-
mentary publication nos. CCDC 153822–153824.
Copies can be obtained free of charge from CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
4
8.25 (d, J(203,205TlꢀH)=99.1 Hz, Fmes). 19F-NMR: l
4
−61.64 (d, J(203,205TlꢀF)=70.4 Hz, 6Fo), −64.04 (d,
6J(203,205TlꢀF)=22.8 Hz, 3Fp). Anal. Calc. for
C27H6F27Tl: C, 30.95; H, 0.6. Found: C, 30.75; H, 0.8%.
LSIMS (m/z, %, assignment): 767 (100, [M−(Fmes)]+).

M. Bardaj´ı et al. / Journal of Organometallic Chemistry 648 (2002) 1–7
7
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