Structural characterization of silver(I) complexes [Ag(O3SCF3)(L)] (L = PPh3, PPh2Me, SC4H8) and [AgL(n)](CF3SO3) (n = 2-4), (L = PPh3, PPh2Me)

Article abstract of DOI:10.1016/S0020-1693(00)00052-9

We have studied the solution and some solid state structures of a series of trifluoromethanesulfonate silver(I) complexes, namely of formula [Ag(O₃SCF₃)(L)] (L = PPh₃, PPh₂Me, SC₄H₈) and [AgL(n)](CF₃SO₃) (n = 2-4, L = PPh₃, PPh₂Me). The solution behaviour is as expected for mononuclear silver species, although polynuclear species can not be totally ruled out in non-coordinating solvents. The solid state structures display a wide variety of nuclearities, silver co-ordination numbers and trifluoromethanesulfonate co-ordination modes, depending on the ligand L. Thus, for complexes of empirical formula [Ag(O₃SCF₃)(L)], the crystal structure of [Ag(O₃SCF₃)(PPh₃)] is a trimer with bridging triflates; the molecular structure of [Ag(O₃SCF₃)(PPh₂Me)] shows tetranuclear complexes with a 'chair' geometry, further linked into chains by Ag-phenyl interactions; and [Ag(O₃SCF₃)(tht)] (tht = SC₄H₈) crystallizes in infinite chains. For complexes of formula [Ag(O₃SCF₃)(L)₂], the PPh₃ derivative is a dimer with two bridging triflates, and the PPh₂Me derivative is a monomer. (C) 2000 Elsevier Science S.A.

Full text of DOI:10.1016/S0020-1693(00)00052-9

www.elsevier.nl/locate/ica
Inorganica Chimica Acta 304 (2000) 7–16
Structural characterization of silver(I) complexes [Ag(O3SCF3)(L)]
(L=PPh3, PPh2Me, SC4H8) and [AgLn](CF3SO3) (n=2–4),
(L=PPh3, PPh2Me)
Manuel Bardaj´ı a, Olga Crespo a, Antonio Laguna a,*, Axel K. Fischer b
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
b Chemisches Institut, Uni6ersita¨t Magdeburg, Uni6ersita¨tsplatz 2, 39106 Magdeburg, Germany
Received 7 October 1999; accepted 6 December 1999
Abstract
We have studied the solution and some solid state structures of a series of trifluoromethanesulfonate silver(I) complexes, namely
of formula [Ag(O3SCF3)(L)] (L=PPh3, PPh2Me, SC4H8) and [AgLn](CF3SO3) (n=2–4, L=PPh3, PPh2Me). The solution
behaviour is as expected for mononuclear silver species, although polynuclear species can not be totally ruled out in
non-coordinating solvents. The solid state structures display a wide variety of nuclearities, silver co-ordination numbers and
trifluoromethanesulfonate co-ordination modes, depending on the ligand L. Thus, for complexes of empirical formula
[Ag(O3SCF3)(L)], the crystal structure of [Ag(O3SCF3)(PPh3)] is a trimer with bridging triflates; the molecular structure of
[Ag(O3SCF3)(PPh2Me)] shows tetranuclear complexes with a ‘chair’ geometry, further linked into chains by Ag–phenyl
interactions; and [Ag(O3SCF3)(tht)] (tht=SC4H8) crystallizes in infinite chains. For complexes of formula [Ag(O3SCF3)(L)2], the
PPh3 derivative is a dimer with two bridging triflates, and the PPh2Me derivative is a monomer. © 2000 Elsevier Science S.A. All
rights reserved.
Keywords: Crystal structures; Silver complexes; Trifluoromethanesulfonate complexes; Phosphine complexes
sulfonate anion (CF3SO3−) is not an oxidising anion
and therefore is safer to handle. Furthermore, it is more
1. Introduction
stable to hydrolysis than tetrafluoroborate or hexa-
fluorophosphate [3].
Complexes of stoichiometry AgYL, where Y is a
poorly co-ordinating anion such as ClO4−, BF4−
,
NO3− or PF6−, have been extensively used either to
exchange a halide for the ligand L in another metal
complex (by precipitation of AgX), or to form poly-
metallic clusters incorporating the unit AgL (in this
case L is usually a phosphine) [1].
During the last few years we have used these trifl-
uoromethanesulfonate silver(I) salts widely as reagents
[4], but no studies of their structure, either in solution
or in the solid state, have been carried out. In this
paper we report the structural characterization of
[Ag(O3SCF3)(L)] (L=PPh3, PPh2Me, SC4H8) and
[AgLn](CF3SO3) (n=2–4, L=PPh3, PPh2Me), includ-
ing X-ray diffraction studies of [Ag(O3SCF3)(L)] (L=
PPh3, PPh2Me, SC4H8) and [Ag(O3SCF3)L2] (L=PPh3,
PPh2Me). The crystal structures show a wide variety of
nuclearities (monomeric, dimeric, trimeric, tetrameric
and polymeric), co-ordination numbers at the silver
centre (silver co-ordinated to three, four or five donor
atoms) and various co-ordination modes of the triflate
ligand.
Nitrate or perchlorate derivatives are potentially ex-
plosive and their use should be accordingly restricted
[2]. Unlike perchlorate or nitrate, the trifluoromethane-
* Corresponding author. Tel.: +34-976-761 185; fax: +34-976-
761 187.
E-mail address: alaguna@posta.unizar.es (A. Laguna)
0020-1693/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(00)00052-9

8
M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
2. Results and discussion
different phosphorus/oxygen ratio in the co-ordina-
tion sphere because this variation of J was found in
the solid-state 31P NMR spectra of a series of nitrate
phosphine silver(I) complexes [6]. The spectra of com-
plexes [AgL3](CF3SO3] show an equilibrium between
the tris(phosphine) complex as the main derivative
and minor amounts of the bis(phosphine) and the
tetrakis(phosphine) derivatives. This has been already
described in similar complexes with other anions
[5a,5b]. An excess of phosphine added to a CDCl3
solution of 4 (8) at −60°C shows in the phosphorus
spectrum a mixture of 4 (or 8) and free phosphine,
which confirms that [Ag(PR2R%)5]+ is not formed.
Their dichloromethane solutions behave as non
conductors for complexes 1, 5 and 9, and as conduc-
tors for the others. In acetone solution all of them
behave as conductors because of the replacement of
triflate by solvent molecules for complexes 1, 5 and 9.
The liquid secondary ion mass spectra (LSIMS+) al-
ways show mono- and bisphosphine cations as the
most intense peaks although peaks coming from dinu-
clear fragments are observed for 1, 5 and 6. For 9
the base peak is [Ag]+.
In conclusion, these experiments indicate a be-
haviour typical of mononuclear complexes in co-ordi-
nating solvents. In non-coordinating solvents the
complexes are probably mononuclear although
polynuclear species can not be totally ruled out: for
instance the tetranuclear solid state structure of 5 (see
the following description) is consistent with the solu-
tion behaviour; on the contrary the reported [7] trinu-
clear solid state structure of 1 is not consistent
because implies two different kind of phosphorus.
The reaction between AgCF3SO3 and the ligand in
the adequate molar ratio (0.97, 2, 3 or 4) leads to
[Ag(O3SCF3)(L)] (L=PPh3, PPh2Me, tht) or
[AgLn](CF3SO3) (L=PPh3, PPh2Me; n=2–4) as
white solids. For n=1 a slight excess of silver is used
to avoid the formation of [AgL2]+.
2.1. Solution studies
The solution structure was firstly studied by means
of NMR experiments. The fluorine spectra show a
constant resonance at about −78.6 ppm for the trifl-
ate group for all the complexes even at −60°C, so
we cannot distinguish between ionic or covalent trifl-
ate. In the proton spectra only the ligand resonances
are seen: phenyl for complexes 1–4, phenyl and
methyl for complexes 5–8, tetrahydrothiophene as
two multiplets at 3.22 and 2.11 ppm for complex 9
(this complex is poorly soluble in chloroform, so the
NMR spectra were carried out in deuteroacetone).
The 31P{1H} NMR spectra at room temperature (r.t.)
show that these complexes are fluxional and therefore
only broad resonances are observed even if a mixture
of complexes is run (except for complex 2 whose
spectrum is already resolved at r.t.). This kind of
fluxionality is typical in the co-ordination chemistry
of silver and can be attributed to exchange phenom-
ena involving the neutral ligands. This process can be
stopped at low temperature to give a unique kind of
phosphorus. Table 1 shows the chemical shift of the
pure complexes at 18 and −60°C and the coupling
constants AgꢀP, which transform a singlet into two
doublets. The remarkably large difference between
coupling constants AgꢀP with changing phosphine
number, from approximately 241 to 860 Hz, has been
attributed to the different s contribution to the hy-
bridization at the silver centres and to the corre-
spondingly different PꢀAgꢀP angles [5] but also to the
2.2. Solid state studies
It has been reported that [Ag(OClO3)(PR3)] com-
plexes have a two-coordinated structure in the solid
state, based on their split perchlorate bands in the IR
spectra; similar results were reported for [Ag{P(t-
Bu)3}(X)] (e.g. X=Cl, Br, SCN, ClO4) complexes [8].
Infrared spectra, which could in principle be used to
distinguish covalent and ionic trifluoromethanesul-
fonate, are not very useful because unambiguous as-
signments of vibrational modes are not easy, because
of overlap of CF3, SO3 and PPh3 vibrational mode
[3].
Table 1
31P{1H} NMR data for complexes [AgLn](CF3SO3) (n=1–4, L=
PPh3 (1–4), PPh2Me (5–8))
Compound l(18°C)
l(−60°C) 1J(109AgꢀP, 107AgꢀP)
1
2
3
4
5
6
7
8
16.8
15.3
11.6
11.2
5.8
−3.8
−4.0
−8.4
−12.8
859.9, 745.9
558.3, 484.7
365.3, 320.4
240.6
637.8
563.6, 522.3
345.6
14.0, 10.3 a
10.2
The best way to determine the nuclearity and the
geometry of these complexes in the solid state is by
X-ray diffraction studies. Crystals of 1, 2, 5, 6 and 9
8.3
−3.3
−4.1
−9.2
−12.8
were
grown
by
slow
evaporation
of
a
dichloromethane or acetone solution or by slow diffu-
sion of diethyl ether into a dichloromethane or ace-
tone solution. These studies show a much more
complicated situation in the solid state, different for
every complex.
240.7
a In this case the AgꢀP coupling is visible at r.t., so instead of two
broad signals it could be expressed as: l=12.1 ppm with 1J(AgꢀP)=
450.3 Hz.

M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
9
2.2.1. Crystal structures of [Ag(O3SCF3)L] (L=PPh3
(1), PPh2Me (5), SC4H8 (9))
Compound 1 (Fig. 1, Table 2) is a trinuclear deriva-
tive in which three AgPPh3 units are bridged by triflate
anions; the asymmetric unit consists of one trimer. The
triflate involving S(1) uses only one donor oxygen atom
O(1), which bridges two silver centres, whereas the
triflate involving S(3) utilises all its oxygen donors O(7),
O(8) and O(9) to connect all three silver centres. The
triflate anion centred on S(2) is disordered over two
positions with different co-ordination to silver, with site
occupation factors in the ratio approximately 4:1; the
minor component (Fig. 2) will not be discussed in
detail, but the main difference is that two of the triflate
ligands bridge the three silver centres by different oxy-
gen atoms. A structural study of compound 1 has been
published [7]. The compound also crystallizes in the
monoclinic P21/n system and the compound exhibits
also a trimeric nature but two trimeric molecules that
are conformational isomers are present instead of one
in our study. The AgꢀP distances found for the tetraco-
ordinate silver centers lie in the narrow range from
Fig. 1. Molecular structure of the major disorder component in
compound 1 with the atom numbering scheme. Phenyl hydrogen
atoms are omitted for clarity. Ellipsoids represent 50% probability
levels.
,
2.3619(10) to 2.3736(10) A. These distances are of the
order of those found in [Ag4Cl4(PPh3)4] [9] (average
Table 2
,
Selected bond lengths (A) and angles (°) for 1
,
2.379 A), where the silver atoms are tetra-coordinated,
Ag(1)ꢀO(1)
Ag(1)ꢀP(1)
Ag(1)ꢀO(7)
Ag(1)ꢀO(4)
Ag(2)ꢀO(1)
Ag(2)ꢀP(2)
Ag(2)ꢀO(8)
Ag(2)ꢀO(4)
Ag(3)ꢀO(9)
Ag(3)ꢀP(3)
Ag(3)ꢀO(5)
P(1)ꢀC(31)
P(1)ꢀC(11)
P(1)ꢀC(21)
P(2)ꢀC(41)
2.357(2)
2.3717(9)
2.439(2)
2.572(3)
2.339(2)
P(2)ꢀC(61)
P(2)ꢀC(51)
P(3)ꢀC(91)
P(3)ꢀC(81)
P(3)ꢀC(71)
1.819(4)
1.823(4)
1.816(3)
1.823(4)
1.826(4)
1.427(3)
1.430(3)
1.470(2)
1.432(3)
1.441(2)
1.454(2)
1.433(4)
1.436(5)
1.447(4)
,
or [Ag4Cl4(dppm)2] [10] (2.366(2) A for three-coordi-
,
nated, 2.379(2) A for tetra-coordinated) but shorter
than those found in the reported structural study for 1
[7] (range 2.327(5)–2.341(5) A), in other complexes of
stoichiometries [Ag4X4(PR3)4], as for example
[AgX(PR3)]4 [11] (X=Br, 2.372(3)—2.386(3) A, X=I,
2.455(5)–2.466(5) A), in [Ag(dppf)(PPh3)]ClO4 (dppf=
1,2-bis(diphenylphosphino)ferrocene) [12], 2.4386(13)–
2.4870(12) A with a trigonal silver centre, or in
tetrahedral derivatives such as [Ag(PPh3)4]ClO4 (1×
2.650, 3×2.668(5) A) [13].
Possible CꢀH···O hydrogen bonds, involving H···O
distances from 2.38 to 2.42 A, are shown in Table 3.
A change of phosphine to PPh2Me (compound 5)
results in a different structure in the solid state, with
varying levels of complexity. The asymmetric unit con-
tains two silver centres, bridged by one oxygen atom
(O(1) and O(4)) from each of the two triflate ligands,
thus forming four-membered Ag2O2 rings that are es-
sentially planar (fold angle 3° about the O···O axis) as
in [Ag(CO2Me)(PPh3)]2 [14]. These dinuclear units are
connected over an inversion centre by additional
Ag(1)ꢀO(5) bonds, thus forming tetranuclear assemblies
at the secondary level (Fig. 3). Such tetrasilver groups,
exhibiting a ‘chair’ geometry, are well-known for com-
plexes such as [AgX(PR3)]4 (where R=Et or Ph and
X=halide) [11] or in the complex [Ag4{SC2B10H10}2-
(O3SCF3)2(PPh3)4] [4b], which contains two [Ag-
(S2C2B10H11)(PPh3)2] units linked through two further
AgꢀS bonds and triflate oxygens chelating the silver
centres. In these associations two of the four silver
,
2.3619(10) S(1)ꢀO(3)
2.483(2)
2.509(3)
2.250(2)
S(1)ꢀO(2)
S(1)ꢀO(1)
S(3)ꢀO(8)
,
,
2.3736(10) S(3)ꢀO(7)
2.476(9)
1.818(3)
1.819(4)
1.821(3)
1.818(4)
S(3)ꢀO(9)
S(2)ꢀO(6)
S(2)ꢀO(5)
S(2)ꢀO(4)
,
,
,
O(1)ꢀAg(1)ꢀP(1)
O(1)ꢀAg(1)ꢀO(7)
P(1)ꢀAg(1)ꢀO(7)
O(1)ꢀAg(1)ꢀO(4)
P(1)ꢀAg(1)ꢀO(4)
O(7)ꢀAg(1)ꢀO(4)
O(1)ꢀAg(2)ꢀP(2)
O(1)ꢀAg(2)ꢀO(8)
P(2)ꢀAg(2)ꢀO(8)
O(1)ꢀAg(2)ꢀO(4)
P(2)ꢀAg(2)ꢀO(4)
O(8)ꢀAg(2)ꢀO(4)
O(9)ꢀAg(3)ꢀP(3)
O(9)ꢀAg(3)ꢀO(5)
P(3)ꢀAg(3)ꢀO(5)
C(31)ꢀP(1)ꢀC(11)
C(31)ꢀP(1)ꢀC(21)
C(11)ꢀP(1)ꢀC(21)
C(31)ꢀP(1)ꢀAg(1)
C(11)ꢀP(1)ꢀAg(1)
S(2)ꢀO(4)ꢀAg(1)
140.42(6)
88.19(8)
124.45(6)
69.45(9)
130.11(7)
82.81(9)
147.51(6)
86.27(8)
107.18(6)
70.86(9)
139.52(8)
C(21)ꢀP(1)ꢀAg(1)
C(41)ꢀP(2)ꢀC(61)
C(41)ꢀP(2)ꢀC(51)
C(61)ꢀP(2)ꢀC(51)
C(41)ꢀP(2)ꢀAg(2)
C(61)ꢀP(2)ꢀAg(2)
C(51)ꢀP(2)ꢀAg(2)
C(91)ꢀP(3)ꢀC(81)
C(91)ꢀP(3)ꢀC(71)
C(81)ꢀP(3)ꢀC(71)
C(91)ꢀP(3)ꢀAg(3)
120.60(11)
104.54(16)
104.47(17)
104.12(16)
108.25(12)
112.72(12)
121.27(12)
105.38(16)
106.63(16)
105.37(16)
114.27(12)
110.29(11)
114.15(12)
122.08(13)
117.56(13)
80.11(10) C(81)ꢀP(3)ꢀAg(3)
153.25(7)
93.5(3)
C(71)ꢀP(3)ꢀAg(3)
S(1)ꢀO(1)ꢀAg(2)
S(1)ꢀO(1)ꢀAg(1)
113.2(3)
104.94(16) Ag(2)ꢀO(1)ꢀAg(1) 113.02(10)
105.64(16) S(3)ꢀO(7)ꢀAg(1)
102.47(16) S(3)ꢀO(8)ꢀAg(2)
110.19(11) S(3)ꢀO(9)ꢀAg(3)
111.68(12) S(2)ꢀO(4)ꢀAg(2)
136.41(15)
139.86(16)
131.86(15)
121.81(19)
123.6(2)
Ag(2)ꢀO(4)ꢀAg(1) 100.84(10)

10
M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
nuclei (in 5 these are Ag(1) and its symmetry equiva-
lent) are tetra-coordinated, although the geometry at
the silver centres is necessarily very distorted because of
the restrictions imposed by the four-membered ring
(steric effects of the bulky ligands may also play a role).
Selected bond lengths and angles are shown in Table 4.
The angles OꢀAgꢀO in 5 are 73.51(7) and 74.83(7)°,
with PꢀAgꢀO from 122.50(5) to 147.79(5)°. The AgꢀP
,
bond lengths in 5, 2.3628(11) and 2.3731(19) A, com-
pare well with those in 1. The AgꢀO distances range
,
from 2.3731(19) to 2.573(2) A.
The unexpected tertiary level involves contacts of the
,
form Ag···phenyl (AgꢀC(44)=2.721(3) A), forming a
polymeric chain. This contact is not of the usual
Fig. 3. Tetranuclear assemblies in compound 5 with the atom num-
bering scheme. Phenyl hydrogen atoms are omitted for clarity. Ellip-
soids represent 50% probability levels.
Table 4
a
,
Selected bond lengths (A) and angles (°) for 5
Ag(1)ꢀP(1)
Ag(1)ꢀO(5)c1
Ag(1)ꢀO(4)
Ag(1)ꢀO(1)
Ag(2)ꢀO(1)
Ag(2)ꢀP(2)
Ag(2)ꢀO(4)
2.3637(10) Ag(2)ꢀC(44)c2
2.3731(19) S(1)ꢀO(2)
2.721(3)
1.421(2)
1.425(2)
1.471(2)
1.431(2)
1.446(2)
1.458(2)
2.464(2)
2.478(2)
S(1)ꢀO(3)
S(1)ꢀO(1)
2.2792(19) S(2)ꢀO(6)
2.3628(11) S(2)ꢀO(5)
2.573(2)
S(2)ꢀO(4)
P(1)ꢀAg(1)ꢀO(5)c1 139.49(5) P(2)ꢀAg(2)ꢀC(44)c2 108.91(8)
P(1)ꢀAg(1)ꢀO(4)
O(5)c1ꢀAg(1)ꢀO(4) 81.60(7) S(1)ꢀO(1)ꢀAg(2)
P(1)ꢀAg(1)ꢀO(1) 122.63(5) S(1)ꢀO(1)ꢀAg(1)
133.57(5) O(4)ꢀAg(2)ꢀC(44)c2 90.21(8)
119.67(11)
126.84(11)
110.08(8)
132.40(11)
114.55(10)
101.47(7)
Fig. 2. Molecular structure of the minor disorder component (primed
atoms) in compound 1. Phenyl rings are omitted for clarity.
O(5)c1ꢀAg(1)ꢀO(1) 81.35(7) Ag(2)ꢀO(1)ꢀAg(1)
O(4)ꢀAg(1)ꢀO(1)
O(1)ꢀAg(2)ꢀP(2)
O(1)ꢀAg(2)ꢀO(4)
P(2)ꢀAg(2)ꢀO(4)
73.51(7) S(2)ꢀO(4)ꢀAg(1)
147.79(5) S(2)ꢀO(4)ꢀAg(2)
74.83(7) Ag(1)ꢀO(4)ꢀAg(2)
122.50(5) S(2)ꢀO(5)ꢀAg(1)c1 125.65(11)
Table 3
,
Possible CꢀH···O hydrogen bonds (A and °)
O(1)ꢀAg(2)ꢀC(44)c2 96.98(9)
DꢀH···A
d(DꢀH) d(H···A) d(D···A) B(DHA)
a Symmetry transformations used to generate equivalent atoms:
c1 −x+1, −y+1, −z+2 c2 −x+2, −y, −z+2.
Compound 1:
C(34)ꢀH(34)···O(3)c1 0.95
2.42
2.37
3.197(5) 138.7
3.246(11) 152.4
C(66)ꢀH(66)···O(5)
0.95
Ag···(aromatic bond) type, such as in the well-known
C(16)ꢀH(16)···O(6)
0.95
2.38
3.287(5) 158.5
AgClO4ꢀbenzene complex [15], because the Ag···C con-
Symmetry transformations used to generate equivalent atoms:
c1 x, y, z+1
Compound 9:
C(4)ꢀH(4A)···O(3)
,
tacts to the neighboring C atoms are both \3 A. The
absence of such contacts for 1 may be attributed to the
more bulky nature of the phosphine group. There are
0.99
2.51
3.465(4) 162.7
,
no H···O contacts shorter than 2.6 A.
Compound 6:
Compound 9 exhibits a very different structure. The
asymmetric unit (Fig. 4) is the monomeric formula unit.
The silver centre is co-ordinated to a tetrahydrothio-
C(1)ꢀH(1A)···O(1)c1 0.98
C(44)ꢀH(44)···O(2)c2 0.95
C(24)ꢀH(24)···O(3)c3 0.95
2.50
2.54
2.47
3.441(4) 162.1
3.311(4) 138.9
3.410(4) 171.9
,
phene sulfur atom (AgꢀS(1)=2.4897(9) A) and a trifl-
Symmetry transformations used to generate equivalent atoms:
c1 −x+1/2, y+1/2, −z+3/2
c2 −x+1, −y+1, −z+1
ate oxygen atom (AgꢀO 2.4963(9), S(1)ꢀAgꢀO(1)=
111.42(8)°). It completes its environment (Fig. 4) firstly
via a sulfur atom of another tetrahydrothiophene group
c3 x−1, y, z
,
(AgꢀS(1%)=2.4963(2) A), resulting in infinite linear

M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
11
Fig. 4. Detail of the polymeric ribbons in compound 9 with the atom numbering scheme. Ellipsoids represent 50% probability levels. Weaker
AgꢀO bonds (see text) are indicated by dashed bonds.
,
weaker silver-oxygen bonds (2.613(2), 2.812(3) A) to
centres in the same manner. Selected bond lengths and
oxygens of two triflate ligands of a neighboring chain,
thus forming a ribbon structure. The co-ordination
geometry at silver is to a good approximation square
pyramidal, with O1 as the apex; the mean deviation of
the atoms S1, S1%, O2%, O3% from the basal plane is only
angles are shown in Table 6. The AgꢀP distances
,
(2.4321(12) and 2.4339(12) A) compare well with those
mentioned above for [Ag(dppf)(PPh3)]ClO4 or in tetra-
hedral silver derivatives as [Ag(phen){(PPh2)2C2B10H10}]-
,
0.06 A, and the angle between the AgꢀO(1) bond and
Table 5
the normal to the base is 6°. Selected bond lengths and
angles are shown in Table 5. The AgꢀS distances com-
pare well with those in other related derivatives such as
a
,
Bond lengths (A) and angles (°) for 9
AgꢀO(1)
AgꢀS(1)
2.450(3)
2.4897(9)
2.4963(9)
2.613(3)
2.812(3)
1.831(4)
1.848(3)
1.437(3)
1.438(3)
S(2)ꢀO(3)
S(2)ꢀC(5)
F(1)ꢀC(5)
F(2)ꢀC(5)
F(3)ꢀC(5)
C(1)ꢀC(2)
C(2)ꢀC(3)
C(3)ꢀC(4)
1.445(3)
1.813(4)
1.333(4)
1.325(4)
1.330(4)
1.523(5)
1.518(6)
1.508(5)
,
[Ag2{S2C2(CN)2}(PPh3)4] [16] (2.568(7), 2.653(7) A) or
the shortest distances in [Ag6{SC6H4Cl)6(PPh3)5] [17]
(2.407(5)–2.484(4) A). Longer AgꢀS distances have
been observed in tetrahedral silver derivatives such as
[AgBr(18S6)] [18] (18S6=1,4,7,10,13,16-hexathiacy-
clooctadecane) (2.514(1)ꢀ2.636(1) A) or in the deriva-
tive [Ag{(SPPh2)2CH2}{(PPh2)2C2B10H10}]ClO4 (2.540-
AgꢀS(1)c1
AgꢀO(3)c2
AgꢀO(2)c3
S(1)ꢀC(1)
S(1)ꢀC(4)
S(2)ꢀO(2)
S(2)ꢀO(1)
,
,
,
(2)ꢀ2.653(7) A) [19]. Details of a possible hydrogen
O(1)ꢀAgꢀS(1)
111.42(8)
103.19(8)
O(2)ꢀS(2)ꢀO(3) 116.03(17)
O(1)ꢀS(2)ꢀO(3) 113.65(17)
bond C(4)···O(3) are given in Table 3.
O(1)ꢀAgꢀS(1)c1
S(1)ꢀAgꢀS(1)c1
O(1)ꢀAgꢀO(3)c2
S(1)ꢀAgꢀO(3)c2
S(1)c1ꢀAgꢀO(3)c2
O(1)ꢀAgꢀO(2)c3
S(1)ꢀAgꢀO(2)c3
S(1)c1ꢀAgꢀO(2)c3
143.415(19) O(2)ꢀS(2)ꢀC(5) 103.55(17)
108.21(9)
87.28(6)
93.03(7)
98.56(8)
85.21(6)
78.16(6)
O(1)ꢀS(2)ꢀC(5) 103.61(17)
O(3)ꢀS(2)ꢀC(5) 103.21(18)
S(2)ꢀO(1)ꢀAg
2.2.2. Crystal structures of [Ag(O3SCF3)L2] (L=PPh3
(2), PPh2Me (6))
Compound 2 is a dinuclear derivative (Fig. 5) in
which the molecule possesses an inversion centre, and
the silver atoms display distorted tetrahedral co-ordina-
tion geometry. This is a common structural type for
complexes of formula [AgX(PPh3)2] [11a,20,21], al-
though complexes as [Ag(CO2CF3)(PPh3)2] [22],
[Ag(NO2)(PPh3)2] [23] or some adducts with tricyclo-
hexylphosphine salts [24] are monomeric. Each silver
atom is bonded to two triphenylphosphine ligands and
two oxygen atoms of different (but crystallographically
equivalent) triflate ligands. The triflate group is disor-
dered over two positions with occupation factors 0.645,
0.335(4); however, both positions bridge the two silver
C(2)ꢀC(1)ꢀS(1) 104.4(2)
C(3)ꢀC(2)ꢀC(1) 106.5(3)
C(4)ꢀC(3)ꢀC(2) 108.2(3)
C(3)ꢀC(4)ꢀS(1) 105.4(2)
F(2)ꢀC(5)ꢀF(3) 107.0(3)
F(2)ꢀC(5)ꢀF(1) 107.8(3)
F(3)ꢀC(5)ꢀF(1) 107.2(3)
F(2)ꢀC(5)ꢀS(2) 112.5(3)
F(3)ꢀC(5)ꢀS(2) 111.8(3)
F(1)ꢀC(5)ꢀS(2) 110.2(3)
O(3)c2ꢀAgꢀO(2)c3 153.11(9)
C(1)ꢀS(1)ꢀC(4)
C(1)ꢀS(1)ꢀAg
94.67(15)
110.44(12)
108.44(12)
115.04(12)
109.01(12)
116.79(3)
C(4)ꢀS(1)ꢀAg
C(1)ꢀS(1)ꢀAgc4
C(4)ꢀS(1)ꢀAgc4
AgꢀS(1)ꢀAgc4
O(2)ꢀS(2)ꢀO(1)
114.59(17)
a Symmetry transformations used to generate equivalent atoms:
c1: −x+1, y+1/2, −z+3/2; c2: −x+1, −y+1, −z+1; c3: x,
−y+3/2, z+1/2; c4: −x+1, y−1/2, −z+3/2.

12
M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
Fig. 5. Molecular structure of the major disorder component in compound 2 with the atom numbering scheme. Phenyl hydrogen atoms are
omitted for clarity. Ellipsoids represent 50% probability levels.
,
ClO4 (2.463(2), 2.479(2) A). The AgꢀO distances are
3. Experimental
dissimilar; in each disorder component there is one
,
3.1. General
AgꢀO bond of similar length to those in 1 (ca. 2.4 A)
,
and one longer bond (\2.5 A). In view of the disorder,
AgCF3SO3, PPh3, PPh2Me and tht were used as
obtained from commercial sources. Syntheses with
PPh2Me were carried out under an argon atmosphere
CꢀH···O interactions were not investigated.
Despite the similar stoichiometry, compound 6 (Fig.
6) exhibits a different structure in the solid state. It is
simply a monomer in which the metallic centre is
co-ordinated to two PPh2Me ligands and two oxygen
atoms of the triflate group. This is another common
structure for [Ag(PR3)2]X [11,22–25], although the
closely related complex [Ag(PPh2Me)2](ClO4) is linear
at silver [26]. Selected bond lengths and angles are
shown in Table 7. The AgꢀP distances (2.3852(8),
Table 6
a
,
Selected bond lengths (A) and angles (°) for 2
AgꢀO(1%)
AgꢀO(1)
AgꢀP(2)
2.385(13)
2.419(6)
2.4321(12)
2.4330(12)
2.517(11)
2.578(5)
P(1)ꢀC(21)
P(1)ꢀC(1)
P(1)ꢀC(11)
P(2)ꢀC(31)
P(2)ꢀC(51)
P(2)ꢀC(41)
1.821(4)
1.826(4)
1.826(4)
1.819(4)
1.822(4)
1.833(4)
AgꢀP(1)
AgꢀO(3%)c1
,
2.3894(8) A) compare well with those observed in 1,
whereas the AgꢀO bonds (2.775(2), 2.854(2) A) are very
AgꢀO(3)c1
,
O(1%)ꢀAgꢀP(2)
O(1)ꢀAgꢀP(2)
O(1%)ꢀAgꢀP(1)
O(1)ꢀAgꢀP(1)
P(2)ꢀAgꢀP(1)
112.6(3)
101.17(17)
109.9(3)
119.27(17)
131.20(4)
C(51)ꢀP(2)ꢀC(41)
C(31)ꢀP(2)ꢀAg
C(51)ꢀP(2)ꢀAg
C(41)ꢀP(2)ꢀAg
C(2)ꢀC(1)ꢀP(1)
C(6)ꢀC(1)ꢀP(1)
C(16)ꢀC(11)ꢀP(1)
C(12)ꢀC(11)ꢀP(1)
C(26)ꢀC(21)ꢀP(1)
C(22)ꢀC(21)ꢀP(1)
C(32)ꢀC(31)ꢀP(2)
C(36)ꢀC(31)ꢀP(2)
C(42)ꢀC(41)ꢀP(2)
C(46)ꢀC(41)ꢀP(2)
C(56)ꢀC(51)ꢀP(2)
C(52)ꢀC(51)ꢀP(2)
SꢀO(3)ꢀAgc1
S%ꢀO(1%)ꢀAg
103.11(17)
110.48(13)
119.50(14)
112.57(13)
122.5(3)
117.9(3)
118.5(3)
122.9(3)
122.8(3)
118.0(3)
123.3(3)
118.3(3)
123.2(3)
117.7(3)
119.0(3)
122.2(3)
138.9(4)
133.4(9)
162.8(8)
long and presumably weak. Thus the geometry towards
the silver centre could be considered as distorted linear,
with a P(1)ꢀAgꢀP(2) angle of 156.21(3)°, and additional
weak co-ordination to the triflate group. It is possible
that the smaller phosphine allows the co-ordination of
the two oxygens to a silver centre, instead of the
formation of a dinuclear structure in which the triflate
ligands, bridge two silver atoms as in 2. Possible
CꢀH···O hydrogen bonds are listed in Table 4.
It is interesting to notice how the co-ordination ge-
ometries depend on the ligand and the co-ordination
properties of the triflate ligand; for instance,
[Ag(PPh3)n](NO3) (n=1, 2) [25,27] are tetrahedral, but
n=3 is trigonal, and [Ag(P(CH2CH2CN)3)2](NO3) [28]
or [Ag(PPh2Me)2](ClO4) [26] are linear. Structures of
complexes with general formula [Ag(PR3)n]+ (n=3 or
4) are usually mononuclear with a triangular or tetrahe-
dral geometry around the silver centre [6].
O(1%)ꢀAgꢀO(3%)c1 90.9(5)
P(2)ꢀAgꢀO(3%)c1 92.6(3)
P(1)ꢀAgꢀO(3%)c1 109.7(3)
O(1)ꢀAgꢀO(3)c1 94.7(2)
P(2)ꢀAgꢀO(3)c1 103.38(15)
P(1)ꢀAgꢀO(3)c1
C(21)ꢀP(1)ꢀC(1)
C(21)ꢀP(1)ꢀC(11)
C(1)ꢀP(1)ꢀC(11)
C(21)ꢀP(1)ꢀAg
C(1)ꢀP(1)ꢀAg
99.54(16)
105.46(18)
104.88(18)
104.13(17)
118.50(14)
107.74(13)
114.86(13)
105.94(17)
103.85(17)
C(11)ꢀP(1)ꢀAg
C(31)ꢀP(2)ꢀC(51)
C(31)ꢀP(2)ꢀC(41)
S%ꢀO(3%)ꢀAgc1
a Symmetry transformations used to generate equivalent atoms:
c1 −x+1, −y+1, −z.

M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
13
3.2. Synthesis of [Ag(O3SCF3)(PPh3)] (1)
To a diethyl ether solution (5 cm3) of AgCF3SO3 (0.1
g, 0.39 mmol) was added a diethyl ether solution (5
cm3) of triphenylphosphine (0.099 g, 0.38 mmol). A
white solid appeared and the mixture was stirred for
about 1 h protected from light. The white solid was fil-
tered off, washed with diethyl ether (2×3 cm3) and
dried by suction. Yield: 85%. Anal. Calc. for C19H15-
AgF3O3PS: C, 43.95; H, 2.9; S, 6.2. Found: C, 44.3; H,
3.05; S, 5.8%. lH 7.5–7.4 (m, Ph); lF −78.6 (s). Mass
spectrum, m/z (M+, %): 889 ([Ag2(O3SCF3)(PPh3)2]+,
12), 631 ([Ag(PPh3)2]+, 45), 369 ([AgPPh3]+, 100).
\M=104 (acetone), 0.8 (dichloromethane) ohm−1 cm2
mol−1
.
Fig. 6. Molecular structure of complex 6 with the atom numbering
scheme. Ellipsoids represent 50% probability levels.
3.3. Synthesis of [Ag(PPh3)n](CF3SO3) (n=2,3) (2–3)
To a diethyl ether solution (5 cm3) of AgCF3SO3 (0.1
g, 0.39 mmol) was added a diethyl ether solution (5
cm3) of triphenylphosphine (n=2, 0.204 g, 0.78 mmol;
n=3, 0.306 g, 1.17 mmol). Further stages as above.
Yield of 2: 94%. Anal. Calc. for C37H30AgF3O3P2S: C,
56.85; H, 3.85; S, 4.1. Found: C, 56.7; H, 3.6; S, 4.2%.
lH 7.5–7.3 (m, Ph); lF −78.5 (s). Mass spectrum, m/z
(M+, %): 631 ([Ag(PPh3)2]+, 100), 369 ([AgPPh3]+, 89).
\M=115 (acetone), 23 (dichloromethane) ohm−1 cm2
mol−1. Yield of 3: 98%. Anal. Calc. for C55H45AgF3-
O3P3S: C, 63.3; H, 4.35; S, 3.05. Found: C, 62.95; H,
4.3; S, 3.45%. lH 7.4–7.1 (m, Ph); lF −78.6 (s). Mass
spectrum, m/z (M+, %): 893 ([Ag(PPh3)3]+, 3), 631
([Ag(PPh3)2]+, 100), 369 ([AgPPh3]+, 100). \M=135
Table 7
,
Selected bond lengths (A) and angles (°) for 6
AgꢀP(2)
AgꢀP(1)
AgꢀO(1)
AgꢀO(2)
P(1)ꢀC(1)
P(1)ꢀC(21)
P(1)ꢀC(11)
2.3852(8)
2.3894(8)
2.775(2)
2.854(2)
1.816(3)
1.817(3)
1.825(3)
P(2)ꢀC(2)
P(2)ꢀC(31)
P(2)ꢀC(41)
SꢀO(3)
SꢀO(2)
SꢀO(1)
1.809(3)
1.812(3)
1.820(3)
1.429(2)
1.431(2)
1.438(2)
P(2)ꢀAgꢀP(1)
P(2)ꢀAgꢀO(1)
P(1)ꢀAgꢀO(1)
P(2)ꢀAgꢀO(2)
P(1)ꢀAgꢀO(2)
O(1)ꢀAgꢀO(2)
C(1)ꢀP(1)ꢀC(21)
C(1)ꢀP(1)ꢀC(11)
156.21(3)
112.58(5)
91.02(5)
95.58(5)
97.43(5)
50.55(6)
104.55(13)
104.88(13)
C(21)ꢀP(1)ꢀAg
C(11)ꢀP(1)ꢀAg
C(2)ꢀP(2)ꢀC(31)
C(2)ꢀP(2)ꢀC(41)
115.79(9)
110.84(9)
106.55(14)
105.64(13)
(acetone), 54 (dichloromethane) ohm−1 cm2 mol−1
.
C(31)ꢀP(2)ꢀC(41) 103.53(12)
C(2)ꢀP(2)ꢀAg
C(31)ꢀP(2)ꢀAg
C(41)ꢀP(2)ꢀAg
SꢀO(1)ꢀAg
114.87(10)
115.79(9)
109.41(9)
93.57(10)
90.49(10)
3.4. Synthesis of [Ag(PPh3)4](CF3SO3) (4)
C(21)ꢀP(1)ꢀC(11) 107.97(12)
C(1)ꢀP(1)ꢀAg 112.06(10)
SꢀO(2)ꢀAg
To
a
dichloromethane suspension (10 cm3) of
AgCF3SO3 (0.1 g, 0.39 mmol) was added triphenylphos-
phine (0.418 g, 1.6 mmol). After stirring for 2 h pro-
tected from light, the solution was concentrated to
approximately 2 cm3. Addition of diethyl ether (10 cm3)
afforded the product as a white solid, which was filtered
off, washed with diethyl ether (2×3 cm3) and dried by
suction. Yield: 90%. Anal. Calc. for C73H60AgF3O3P4S:
C, 67.15; H, 4.65; S, 2.45. Found: C, 66.95; H, 4.75; S,
2.45%. lH 7.4–7.1 (m, Ph); lF −78.6 (s). Mass spec-
trum, m/z (M+, %): 893 ([Ag(PPh3)3]+, 1), 631
([Ag(PPh3)2]+, 100), 369 ([AgPPh3]+, 98). \M=126
with distilled diethyl ether. IR spectra were recorded on
a Perkin–Elmer 883 spectrophotometer, over the range
4000–200 cm−1
, by using Nujol mulls between
1
polyethylene sheets. H, 19F and 31P{1H} NMR spectra
were recorded on a Varian UNITY 300, Bruker ARX·300
or GEMINI 2000 apparatus in CDCl3 solutions (kept
with Na2CO3), if no other solvent is stated; chemical
shifts are quoted relative to SiMe4 (external, 1H), CFCl3
(external, 19F) and 85% H3PO4 (external, 31P). C, H and
S analyses were performed with a Perkin–Elmer 2400
microanalyzer. Mass spectra were recorded on VG
Autospec LSIMS Technique using 3-nitrobenzylalcohol
as a matrix and a Cesium gun. Conductivities were
measured in acetone or dichloromethane solution (5×
10−4 M) with a Philips PW 9509 apparatus.
(acetone), 61 (dichloromethane) ohm−1 cm2 mol−1
.
3.5. Synthesis of [Ag(PPh2Me)n](CF3SO3) (n=1–4) (5–
8)
To a diethyl ether solution (10 cm3) of AgCF3SO3
(0.05 g, 0.19 mmol) under an argon atmosphere was

14
M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
Table 8
Details of data collection and structure refinement for the complexes 1, 2, 5, 6 and 9
Compound
1
2
5
6
9
Chemical formula
Crystal habit
C57H45Ag3F9O9P3S3
colorless plate
0.7×0.4×0.1
monoclinic
P21/n
13.039(2)
35.541(6)
13.112(2)
90
94.40(2)
90
6058.5(17)
4 (trimers)
1.708
1558.63
3096
−120
56.6
12.2
0.577–0.999
38679
14885
C
74H60Ag2F6O6P4S2 C56H52Ag4F12O12P4S4
C27H26AgF3O3P2
C5H8AgF3O3S2
colorless plate
0.35×0.20×0.06
triclinic
colorless irregular tablet colorless irregular prism colorless plate
0.6×0.4×0.2
triclinic
Crystal size (mm3)
Crystal system
Space group
0.55×0.30×0.20
monoclinic
P21/n
11.293(2)
11.887(3)
21.218(5)
90
101.63(2)
90
2789(11)
4 (monomers)
1.565
657.35
1328
−130
50
9.59
0.48×0.24×0.04
monoclinic
P21/c
11.637(2)
7.9917(10)
12.032(2)
90
114.249(10)
90
1020.3(3)
4
2.247
345.10
672
−110
56.6
(
(
P1
P1
,
a (A)
12.3565(18)
12.5966(16)
13.190(2)
72.097(10)
62.726(10)
70.790(10)
1692.9(4)
1 (dimer)
1.533
1562.96
792
−100
50
8.04
11.717(4)
12.584(4)
12.838(4)
79.11(2)
71.82(2)
64.06(2)
1614.1(19)
1 (tetramer)
1.881
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
U (A )
Z
Dc (g cm−3
M
)
1828.58
904
−130
50
15.17
0.963–0.720
7256
5688
F(000)
T (°C)
2qmax (°)
v (Mo Ka) (cm−1
)
24.07
0.999–0.811
6657
Transmission
Reflections measured
Unique reflections
0.894–1.000
6224
5930
0.792–0.753
6648
4928
2486
Rint
0.0415
0.0466
0.0316
0.0413
0.0726
457
433
0.858
0.0349
0.0243
0.0592
417
0.0218
0.0282
0.0667
336
0.0338
0.0318
0.0753
127
a
R
(F\4|(F))
wR (F2, all reflections) 0.0844
b
Parameters
Restraints
790
49
1.085
0.686
0
0
0
c
S
1.050
0.433
1.043
0.411
1.018
0.665
−3
,
Max Dz (e A
)
0.536
a R(F)=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ.
b wR(F2)=[S{w(Fo2−Fc2)2}/S{w(Fo2)2}]0.5; w−1=|2(Fo2)+(aP)2+bP, where P=[Fo2+2Fc2]/3 and a and b are constants adjusted by the
program.
c S=[S{w(Fo2−Fc2)2}/(n−p)]0.5, where n is the number of data and p the number of parameters.
added methyldiphenylphosphine (n=1, 36 ml, 0.19
mmol; n=2, 73 ml, 0.39 mmol; n=3, 110 ml, 0.58
mmol; n=4, 147 ml, 0.78 mmol). The solution was
stirred for 1 h protected from light and concentrated
to approximately 2 cm3, whereafter the addition of
pentane afforded the complexes as white solids. These
were washed with pentane (2×3 cm3) and dried by
suction. Yield of 5: 73%. Anal. Calc. for
C14H13AgF3O3PS: C, 36.8; H, 2.85; S, 7.0. Found: C,
36.75; H, 2.8; S, 7.15%. lH 7.6-–.4 (m, 10H, Ph),
1.96 (d, 3H, 2JHP=7.4 Hz; Me); lH (−60°C): 1.93
3H, Me); lF −78.5 (s). Mass spectrum, m/z (M+,
%):
765
([Ag2(O3SCF3)(PPh2Me)2]+,
2),
507
([Ag(PPh2Me)2]+, 100), 307 ([AgPPh2Me]+, 100).
\M=116 (acetone), 16 (dichloromethane) ohm−1 cm2
mol−1
.
Yield of 7: 86%. Anal. Calc. for
C40H39AgF3O3P3S: C, 56.0; H, 4.6; S, 3.75. Found: C,
55.95; H, 4.75; S, 3.95%. lH 7.3–7.2 (m, 10H, Ph),
1.75 (d, 3H, 2JHP=3.8 Hz, Me); lH (−60°C): 1.73
(brs, 3H, Me); lF −78.7 (s). Mass spectrum, m/z
(M+,
%):
507
([Ag(PPh2Me)2]+,
94),
307
([AgPPh2Me]+, 100). \M=103 (acetone), 45
(dichloromethane) ohm−1 cm2 mol−1. Yield of 8:
93%. Anal. Calc. for C53H52AgF3O3P4S: C, 60.2; H,
4.95; S, 3.05. Found: C, 59.8; H, 5.3; S, 3.25%. lH
7.4–7.1 (m, 10H, Ph), 1.65 (d, 3H 2JHP=3.8 Hz;
Me); lH (−60°C): 1.52 (brs, 3H, Me); lF −78.6 (s).
Mass spectrum, m/z (M+, %): 507 ([Ag(PPh2Me)2]+,
85), 307 ([AgPPh2Me]+, 100). \M=120 (acetone), 51
2
(d, 3H, JHP=7.2 Hz; Me); lF −78.5 (s). Mass spec-
trum, m/z (M+, %): 765 ([Ag2(O3SCF3)(PPh2Me)2]+,
8), 507 ([Ag(PPh2Me)2]+, 45), 307 ([AgPPh2Me]+,
100). \M=122 (acetone), 1 (dichloromethane) ohm−1
cm2 mol−1
. Yield of 6: 86%. Anal. Calc. for
C27H26AgF3O3P2S: C, 49.35; H, 4.0; S, 4.9. Found: C,
49.4; H, 3.9; S, 4.75%. lH 7.5–7.4 (m, 10H, Ph), 2.07
(d, 3H, 2JHP=4.8 Hz, Me); lH (−60°C): 2.06 (brs,
(dichloromethane) ohm−1 cm2 mol−1
.

M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
15
3.6. Synthesis of [Ag(O3SCF3)(tht)] (9)
Caja de Ahorros de la Inmaculada no. CB4/98 for
financial support.
To a diethyl ether solution (5 cm3) of AgCF3SO3 (0.1
g, 0.39 mmol) was added tetrahydrothiophene (34 ml, 0.38
mmol). Awhitesolidappearedandthemixturewasstirred
for about 1 h protected from light. The white solid was
filtered off, washed with diethyl ether (2×3 cm3) and
dried by suction. Yield: 80%. Anal. Calc. for
C5H8AgF3O3S2: C, 17.4; H, 2.35; S, 18.6. Found: C, 17.45;
H, 2.2; S, 18.25. lH (d6-acetone) 3.22 (m, 4H,
ꢀSꢀCH2ꢀCH2ꢀ), 2.11 (m, 4H, ꢀSꢀCH2ꢀCH2ꢀ); lF −78.7
(s). Mass spectrum, m/z (M+, %): 195 ([Ag(tht)]+, 18),
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Acknowledgements
We thank the Spanish DGICYT (Project PB97-1010-
C02-01), the Fonds der Chemischen Industrie and the
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16
M. Bardaj´ı et al. / Inorganica Chimica Acta 304 (2000) 7–16
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