Synthesis and structural characterization of silver(I) complexes with moon-shaped benzo[1,2-b;4,3-b′]dithiophene phosphine derivative ligands

Article abstract of DOI:10.1016/j.poly.2008.11.013

New silver complexes of general formula [Ag(O₃SCF₃)(PPh₂{bzt})_n] (n = 1-3, bzt = benzo[1,2-b;4,3-b′]dithiophene) have been synthesized and characterized. Spectroscopic studies shown neutral ligand fluxionallity,

Full text of DOI:10.1016/j.poly.2008.11.013

Polyhedron 28 (2009) 239–244
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Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and structural characterization of silver(I) complexes
with moon-shaped benzo[1,2-b;4,3-b0]dithiophene phosphine derivative ligands
a
b
b
M. Helena Garcia a, , Pedro Florindo , M. Fátima M. Piedade , M. Teresa Duarte
*
a Centro de Ciências Moleculares e Materiais, Faculdade de Ciências da Universidade de Lisboa, Ed.C8, Campo Grande, 1749-016 Lisboa, Portugal
b Centro de Química Estrutural, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
a r t i c l e i n f o
a b s t r a c t
Article history:
New silver complexes of general formula [Ag(O3SCF3)(PPh2{bzt})n] (n = 1–3, bzt = benzo[1,2-b;4,3-
b0]dithiophene) have been synthesized and characterized. Spectroscopic studies shown neutral ligand
fluxionallity, typical of silver(I) complexes. The solid state structure of the complexes was determined
by X-ray crystallographic studies, showing a decrease in structure complexity with increasing number
of neutral ligands in silver coordination sphere: [Ag(O3SCF3)(PPh2{bzt})] is a dimer with two bridging tri-
flate anions, further linked into polymeric bidimensional chains along bc plane, through Agꢀ ꢀ ꢀPh close
contacts; Ag(O3SCF3)(PPh2{bzt})2] is also a dimmer with two bridging triflate anions, displaying an inter-
esting packing feature, with zig-zag alignment of bzt groups along direction b; [Ag(O3SCF3)(PPh2{bzt})3] is
a monomer.
Received 12 September 2008
Accepted 7 November 2008
Available online 26 December 2008
Keywords:
Silver complexes
Crystal structures
Trifluoromethanesulfonate complexes
Benzo[1,2-b;4,3-b0]dithiophene
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
in this case, only as P-donor and unravel beautiful and unexpected
solid state packing features for these complexes.
The chemistry of poly-nuclear coordination complexes of coin-
age metals is a field of continuous growing due to the almost
unlimited possibilities of chemical designs, ranging from simple
molecules to polymeric arrangements [1,2]. Within this area, sil-
ver(I) complexes of the type AgX/(PR3)n, where X is a oxyanion
2. Results and discussion
The ligand benzo[1,2-b;4,3-b0]dithiophen-2-diphenylphosphine
(L1) was synthesized based on the procedure reported for the syn-
thesis of the analogue benzo[1,2-b;4,3-b0]dithiophen-2-carbalde-
ꢁ
such as NO3ꢁ, ClO4ꢁ, NO2 and CF3SO3ꢁ, are known to show inter-
esting structural variations arising from different coordination
modes of the anions [3–7]. Despite the intense investigation on
the AgX/(PR3)n complexes, specially for R = Ph [3–7], complexes
of the type AgX/(PR2R0)n were only sporadically investigated
[6,8], nonetheless revealing that the identity of R0 has a large influ-
ence both on silver(I) nuclearity and/or solid state packing fea-
tures. Benzo[1,2-b;4,3-b0]dithiophen-2-diphenylphosphine is an
interesting ligand, in this respect, to study structural features in-
duced by the large volume and moon-shape of the benzo[1,2-
b;4,3-b0]dithiophene (bzt) group and also due to the possibility of
this ligand to act as P,S-donor in a bridging bidentate fashion. In
this paper we report the synthesis and spectroscopic characteriza-
tion (1H, 31P RMN) of novel silver(I) complexes of general formula
[Ag(O3SCF3)(PPh2{bzt})n] (n = 1–3), fully supported by single-crys-
tal X-ray studies to understand the relationships between silver(I)
hyde [9], by generation of the benzodithiophene
n-BuLi and subsequent treatment with (C6H5)2PCl, affording L1 in
good yield (60%), as a colorless oil.
The silver complexes [Ag(CF3SO3)(PPh2{bzt})n] (nAg: n = 1, 2
and 3) were prepared by reaction of AgCF3SO3 and an adequate
molar ratio of L1 (0.96, 2 and 3, respectively), in dichloromethane.
The compounds were obtained as crystalline white solids, stable to
air but slightly unstable to light in solution, soluble in dichloro-
methane, chloroform, acetone, acetonitrile and insoluble in tetra-
hydrofuran, ethyl ether and hydrocarbons.
a-anion with
The 1H NMR spectra of the complexes only show the ligand res-
onances, slightly deshielded upon coordination to the metal center.
For compounds [Ag(CF3SO3) (PPh2 {bzt})] 1Ag, [Ag(CF3-
SO3)(PPh2{bzt})3] 3Ag and for free L1, the resonances of proton H3
are doublets, with coupling constants ranging from 6.8 to
11.2 Hz, attributed to P(–C–C–)H coupling, while it appears as a
singlet in [Ag(CF3SO3)(PPh2{bzt})2] 2Ag.
ꢁ
nuclearity, CF3SO3 coordinating ability and PPh2{bzt} coordina-
tion modes. Also, comparison is made with related compounds to
get some insight on the influence of the bzt group on silver nucle-
arity and solid state packing. Our results show that PPh2{bzt} acts,
Although the 31P NMR spectra of L1 show a resonance at ꢁ17.06
as a sharp singlet, the complexes spectra obtained at room temper-
ature revealed no resonances. This behavior is attributed to compl-
exe’s fluxionallity, due to the exchanging phenomena involving
neutral ligands, typical of silver coordination chemistry [6]. At
* Corresponding author. Tel.: +351 217500972; fax: +351 217500088.
E-mail address: lena.garcia@fc.ul.pt (M.H. Garcia).
0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.11.013

240
M.H. Garcia et al. / Polyhedron 28 (2009) 239–244
Table 1
ꢁ60 °C the spectra are resolved, showing the phosphorus reso-
nances as two doblets, with Ag–P coupling constants ranging from
321.0 to 788.5 Hz, although for 1Ag the second doublet isn’t re-
solved. The large difference between Ag–P coupling constants is
attributed both to the different s contribution to the hybridization
of the silver centers [10] and to the different phosphorus/oxygen
ratio in the silver coordination sphere [11].
Selected bond lengths and angles for compound 1Ag.
Bond lengths (Å)
Ag1–O1
Ag1–O3#1
Ag1–P1
2.3045(17)
2.5028(17)
2.3738(6)
2.687(2)
S1–O1
S1–O2
S1–O3
1.4492(17)
1.425(2)
1.4354(17)
Ag1–C125#2
Bond angles (°)
O1–Ag1–O3#1
P1–Ag1–O3#1
O1–Ag1–P1
O3#1–Ag1–C125#2
P1–Ag1–C125#2
83.49(6)
110.82(4)
147.05(5)
77.28(7)
121.09(6)
O3–S1–O1
S1–O1–Ag1
S1–O3–Ag1#1
O1–Ag1–C125#2
113.83(11)
120.29(10)
147.81(11)
90.45(7)
2.1. Crystallographic studies
X-ray diffraction studies constitute an unambiguous way to
determine both the nuclearity and the geometry of the silver com-
pounds synthesized. In this case, infrared spectra are not useful to
distinguish trifluoromethanesulfonate coordination modes, due to
ambiguity in the attribution of CF3, SO3 and L1 vibrational modes
[12].
Symmetry transformations used to generate equivalent atoms: #1: ꢁx + 1, ꢁy, ꢁz;
#2: x, ꢁy + 1/2, z ꢁ 1/2.
Crystals of compounds 1Ag, 2Ag and 3Ag were obtained by slow
diffusion of n-hexane into dichloromethane solutions. Compound
1Ag crystallizes in a centrosymmetric spatial group (P21/c, mono-
clinic). This compound is a dinuclear derivative of [Ag2(CF3-
SO3)2(PPh2{bzt})2], in which two silver centers are bridged by
two equivalent triflate anions using two donor oxygen atoms,
O(1) and O(21), forming an eight-atom cycle (Fig. 1). Silver atoms
deviate from planarity with the three coordinated atoms.
Table 1 presents selected bond lengths and angles for com-
pound 1Ag. The Ag(1)–P(1) distance is similar to the Ag-P distances
determined for the analogous compounds [Ag(CF3SO3)(PPh3)]
most perpendicular to the Ph ring, with angles between this bond
and other Ph carbon atoms ranging from 81.97° to 101.97°. A sim-
ilar Agꢀ ꢀ ꢀPh close contact was found for compound [Ag(CF3-
SO3)(PPh2Me)] (2.721(3)) [6]. The arrangement of L1 accounts for
the establishment of the Ag(1)ꢀ ꢀ ꢀC(125) short contact: the large
bzt groups are almost perpendicular to the O(1)–Ag(1)–O(21)
plane, minimizing the sterical hindrance on the silver center in
the opposite side; also, a significant difference (approximately
36°) between angles O–Ag–P is verified, thus allowing the align-
ment of Ag(1) with C(125). Each dimeric unit interacts with four
other units, leading to the formation of a bidimensional polymeric
chain along the bc plane, packed along the a direction. This poly-
meric arrangement is illustrated in Fig. 2.
Compound 2Ag is also a dinuclear derivative (Fig. 3) in which
the molecule possesses an inversion center, with silver atoms dis-
playing distorted tetrahedral coordination geometry. Each metal
center is bonded to two phosphorus atoms of L1 and two oxygen
atoms of distinct, but crystallographically equivalent, triflate an-
ions, forming an eight member cycle similar to the one found for
1Ag. This structural arrangement is quite common in complexes
of general formula [AgX(PPh3)2] [6,11]. Table 2 presents selected
(2.3619(10)–2.3736(10) Å)
and
[Ag(CF3SO3)(PPh2Me)]
(2.3628(11)–2.3637(10) Å) [6]; Ag–O distances are also in the
interval verified for the referred compounds: 2.250(2)–2.572(3) Å
and 2.2792(19)–2.573(2) Å, respectively.
Each silver atom of the dimer [Ag2(CF3SO3)2(PPh2{bzt})2] estab-
lishes a short contact with a Ph carbon atom (C(125)) of a distinct
dimer, the distance between the atoms being of 2.688(2) Å. This
contact is not of the usual Agꢀ ꢀ ꢀ(aromatic bond) type, such as in
the AgClO4–benzene complex [13] since Agꢀ ꢀ ꢀC contacts to C neigh-
bor atoms are significantly longer. The Ag(1)ꢀ ꢀ ꢀC(125) contact is al-
Fig. 1. Molecular diagram of 1Ag with 50% thermal ellipsoids, showing the labeling scheme. Hydrogen atoms have been omitted for clarity.

M.H. Garcia et al. / Polyhedron 28 (2009) 239–244
241
Fig. 2. Perspective of the bidimensional polymeric chain of 1Ag along a (left) and c (right).
Fig. 3. Molecular diagram of 2Ag with 40% thermal ellipsoids, showing the labeling scheme. Hydrogen atoms have been omitted for clarity.
bond lengths and angles for compound 2Ag. Both Ag–P (2.439(2)
and 2.434(2) Å) and Ag–O distances are comparable to the ones
found for compound [Ag(O3SCF3)(PPh3)2] (2.409(5) and 2.572(5))
(Ag–P: 2.4321(12) and 2.4339(12); Ag–O: 2.385(13) to 2.578(5)
[6]; Ag–O distances resemble the dissimilarity found in compound
[Ag(O3SCF3)(PPh3)2].
[Ag(O3SCF3)(PPh2{bzt})] (1Ag) have totally different solid state
arrangements ([Ag(O3SCF3)(PPh3)] is trinuclear derivative
[6,14] while 1Ag is bidimensional polymer), compounds
[Ag(O3SCF3)(PPh3)2] and [Ag(O3SCF3)(PPh2{bzt})2] (2Ag) have sim-
ilar arrangements.
a
a
The four bzt groups of each dimer have an almost parallel align-
ment. This parallel alignment between bzt groups is maintained
along direction a, through weak hydrogen bonding between the
Ph groups and fluorine and oxygen atoms of neighbor dimers
(C(225)–H(225)ꢀ ꢀꢀF2 {2.669(6) Å}, (C(113)–H(113)ꢀ ꢀꢀO3 {2.657(5) Å}
Worth noticing the effect of the substitution of one Ph ring by
the larger bzt group: compounds [Ag(O3SCF3)(PPh3)] and
Table 2
and C(114)–H(114)ꢀ ꢀ ꢀF(1) {2.635(6) Å}), forming
a columnar
Selected bond lengths and angles for compound 2Ag.
packing. The column packing along the b direction is made, alter-
nately, between columns symmetrically generated trough an
180° rotation around the a axis in relation to the neighbor ones,
which results in a zig-zag alignment of the bzt groups along b, as
illustrated in Fig. 4.
Bond distances (Å)
Ag1–O1
Ag1–O3
Ag1–P1
Ag1–P2
2.572(5)
2.411(5)
2.439(2)
2.434(2)
S1–O1
S1–O3#1
S1–O2
1.442(5)
1.434(5)
1.414(5)
Compound 3Ag ꢀ 0.5CH2Cl2 crystallizes in the triclinic centro-
Bond angles (°)
O1–Ag1–O3
O1–Ag1–P1
O1–Ag1–P2
O3–Ag1–P1
O3–Ag1–P2
ꢀ
symmetric space group P1. The asymmetric unit (Fig. 5) is the
84.32(15)
112.22(12)
98.11(12)
108.65(13)
117.78(14)
P1–Ag1–P2
126.35(7)
127.1(3)
136.8(3)
114.9(3)
monomeric formula unit with the half solvent molecule of CH2Cl2.
Selected bond lengths and angles are presented in Table 3.
The silver atom is coordinated to three phosphorus atoms of L1
ligands and to an oxygen atom (O1) of trifluoromethanesulfonate,
displaying a distorted tetrahedral coordination. The Ag–P bond
distances range from 2.4780(12) to 2.5113(11) Å and are shorter
S1–O1–Ag1
S1#1–O3–Ag1
O3#1–S1–O1
Symmetry transformations used to generate equivalent atoms: #1: ꢁx + 1, ꢁy,
ꢁz + 1.

242
M.H. Garcia et al. / Polyhedron 28 (2009) 239–244
Fig. 4. Perspective of the supramolecular arrangement of 2Ag, along direction c: dimer alignment along direction a (horizontal) and zig-zag alignment of bzt groups along b
(vertical).
Table 3
than the ones found for compounds [AgX(PPh3)3] (X = Cl: 2.558(5)–
Selected bond lengths and angles for compound 3Ag ꢀ 0.5CH2Cl2.
2.582(4); Br: 2.528(3)–2.549(7); I: 2.544(2)–2.780(3) [15]; NO3:
Bond lengths (Å)
2.525(1)–2.630(2) [11]; CO2C2F5: 2.5432(7)–2.6026(8) Å [16]). P–
Ag–P angles range between 111.49(4) and 124.67(4) Å: the angle
Ag1–O1
Ag1–P1
Ag1–P2
Ag1–P3
2.527(5)
S1–O1
S1–O2
S1–O3
1.414(4)
1.417(4)
1.445(5)
2.4886(12)
2.5113(11)
2.4780(12)
Bond angles (°)
P1–Ag1–P2
P1–Ag1–P3
P2–Ag1–P3
O1–Ag1–P1
O1–Ag1–P2
111.49(4)
124.67(4)
112.28(4)
100.70(13)
97.04(11)
O1–Ag1–P3
S1–O1–Ag1
O1–S1–O2
O1–S1–O3
O2–S1–O3
105.75(12)
151.0(3)
119.0(3)
112.1(3)
113.1(3)
P(1)–Ag(1)–P(3) is higher (ꢂ23 Å) than the other two P–Ag–P an-
gles, minimizing the interaction between L1 ligands and the anion,
and opposite to the longer Ag–P(2) distance, as expected.
3. Experimental
3.1. General procedures
All the experiments were carried out under a dinitrogen atmo-
sphere, using standard Schlenk techniques. All solvents used were
dried using standard methods [17]. AgCF3SO3 and (C6H5)2PCl were
purchased from Aldrich and used without further purification. 1H
and 31P NMR spectra were recorded on a Bruker Avance 400 spec-
trometer at probe temperature, unless stated otherwise. The 1H
NMR (chloroform-d) chemical shifts are reported in parts per mil-
lion (ppm) downfield from internal Me4Si and the 31P NMR (chlo-
roform-d) spectra are reported in ppm downfield from external
standard, 85% H3PO4. Elemental analyses were obtained at
Laboratório de Análises, Instituto Superior Técnico, using a Fisons
Fig. 5. Molecular diagram of 3Ag with 40% thermal ellipsoids, showing the labeling
scheme. Hydrogen atoms have been omitted for clarity.

M.H. Garcia et al. / Polyhedron 28 (2009) 239–244
243
Table 4
Details of data collection and structure refinement for complexes 1Ag, 2Ag and 3Ag.
Compound
1Ag
2Ag
3Ag ꢀ 0.5CH2Cl2
Chemical formula
Formula weight
T (K)
C23H15AgF3O3PS3
631.37
150(2)
C45H30AgF3O3P2S5
1005.80
150(2)
C67.5H45AgClF3O3P3S7
1421.68
150(2)
Wavelength
Crystal system
Space group
a (Å)
b (Å)
c (Å)
0.71073
monoclinic
P21/c
11.2634(9)
18.7654(13)
11.4873(8)
90
100.619(4)
90
2386.4(3)
4
0.71073
monoclinic
P21/n
12.631(4)
22.428(7)
15.754(5)
90
103.18(2)
0.71073
triclinic
ꢀ
P1
11.2932(7)
12.2422(8)
24.8700(16)
80.429(4)
86.819(4)
65.425(4)
3083.0(3)
2
a
(°)
b (°)
c
(°)
90
4346(2)
4
V (Å3)
Z
Z’
0.5
1.757
1.222
0.5
1.537
0.831
1
Dcalc (g cmꢁ3
)
1.531
0.743
Absorption coefficient (mmꢁ1
)
F(000)
1256
2032
1444
h Range for data collection (°)
Limiting indices
Reflections collected/unique (Rint
Completeness to theta
Refinement method
2.82–26.37
1.87–27.70
1.91–27.60
ꢁ14 6 h 6 14,ꢁ23 6 k 6 23,ꢁ14 6 l 6 14
70062/4864 (0.0531)
26.37 (99.8%)
ꢁ15 6 h 6 16,ꢁ28 6 k 6 28,ꢁ20 6 l 6 20
44956/10055 (0.1594)
27.70 (98.5%)
ꢁ14 6 h 6 14,ꢁ15 6 k 6 15,ꢁ32 6 l 6 29
42714/13939 (0.0693)
27.60 (97.5%)
)
full-matrix least-squares on F2
4864/0/307
full-matrix least-squares on F2
10055/0/532
full-matrix least-squares on F2
13939/0/768
Data/restraints/parameters
Goodness-of-fit on F2
1.024
0.994
1.026
Final R indices [I > 2
r(I)]
R1 = 0.0267,wR2 = 0.0592
0.838/ꢁ0.441
R1 = 0.0689,wR2 = 0.1612
0.750/ꢁ1.107
R1 = 0.0575,wR2 = 0.1295
1.746/ꢁ0.990
Largest difference in peak/hole (e Åꢁ3
)
Instruments EA1108 system. Data acquisition, integration and
handling were performed using a PC with software package EA-
GER-200 (Carlo Erba Instruments).
3.3.1. [Ag(CF3SO3)(PPh2{bzt})] (1Ag)
Yield: 94%. White. Anal. (%): Calc. for C23H15S3O3PF3Ag: C, 43.75;
H, 2.39; S, 15.24. Found: C, 44.12; H, 2.39; S, 15.92. 1H NMR: 7.50
(m, 6H, PPh2), 7.59 (m, 4H, PPh2), 7.61 (d, 1H, H10, JHH = 4.8 Hz),
7.70 (d, 1H, H7, JHH = 8.8 Hz), 7.76 (d, 1H, H11, JHH = 5.2 Hz), 7.88
(d, 1H, H6, JHH = 8.4 Hz), 8.39 (d, 1H, H3, JHP = 11.2 Hz). 31P NMR
(ꢁ60 °C): 3.23 (d, J(109Ag–P) = 788.5 Hz).
3.2. Synthesis of benzo[1,2-b;4,3-b0]dithiophen-2-diphenylphosphine
(L1)
To a THF solution (15 mL) of benzo[1,2-b;4,3-b0]dithiophene
(0.19 g, 1 mmol) cooled at ꢁ78 °C, was slowly added a 2.0 M n-BuLi
pentane solution (0.55 mL, 1.1 mmol). The mixture was stirred at
ꢁ78 °C for 5 min and for 15 min at room temperature. The result-
ing yellow solution was cooled at ꢁ78 °C and treated with Ph2PCl
(0.22 mL, 1.2 mmol). After 1 h under agitation at ꢁ78 °C, the solu-
tion was warmed to room temperature and quenched with a satu-
rated solution of NH4Cl (5 mL). The THF was removed under
reduced pressure, the crude material was taken up with CH2Cl2
(20 mL) and washed with saturated aqueous solution of NH4Cl
(3 ꢃ 10 mL) and water (3 ꢃ 10 mL). The organic phase was dried
over MgSO4, the solvent was removed under reduced pressure
and the crude material was purified by means of flash column
chromatography (eluent: light petroleum/CH2Cl2 4:1). Yield: 60%.
Colorless oil. Anal. (%): Calc. for C22H15PS2: C, 70.56; H, 4.04; S,
17.13. Found: C, 70.01; H, 3.95; S, 17.35. 1H NMR: 7.30 (m, 6H,
Ph), 7.38 (m, 4H, Ph), 7.47 (d, 1H, H10, JHH = 5.2 Hz), 7.59 (d, 1H,
H11, JHH = 5.2 Hz), 7.62 (d, 1H, H7, JHH = 8.4 Hz), 7.71 (d, 1H, H6,
JHH = 8.4 Hz), 8.02 (d, 1H, H10, JHP = 6.8 Hz). 31P NMR: ꢁ17.06 (s).
3.3.2. [Ag(CF3SO3)(PPh2{bzt})2] (2Ag)
Yield: 89%. White. Anal. (%): Calc. for C45H30S5O3P2F3Ag ꢀ
0.3CH2Cl2: C, 52.76; H, 2.99; S, 15.54. Found: C, 52.84; H, 3.11; S,
15.60. 1H NMR: 7.38 (m, 4H, PPh2), 7.48 (m, 2H, PPh2), 7.53 (d,
1H, H10, JHH = 5.2 Hz), 7.59 (m, 4H, PPh2), 7.63 (d, 1H, H11
,
JHH = 4.8 Hz), 7.64 (d, 1H, H6, JHH = 8.8 Hz), 7.85 (d, 1H, H6,
JHH = 8.8 Hz), 8.46 (s, 1H, H3). 31P NMR (ꢁ60 °C): 0.79 (dd,
J(109Ag–P, 107Ag–P) = 553.3, 488.4 Hz).
3.3.3. [Ag(CF3SO3)(PPh2{bzt})3] (3Ag)
Yield: 82%. White. Anal. (%): Calc. for C67H45S7O3P3F3Ag ꢀ
0.4CH2Cl2: C, 57.24; H, 3.26; S, 15.87. Found: C, 57.12; H, 3.32; S,
15.88. 1H NMR: 7.08 (m, 4H, PPh2), 7.23 (m, 2H, PPh2), 7.38 (d,
1H, H10, JHH = 5.6 Hz), 7.40 (d, 1H, H11, JHH = 5.6 Hz), 7.42 (m, 4H,
PPh2), 7.51 (d, 1H, H6, JHH = 8.8 Hz), 7.75 (d, 1H, H6, JHH = 8.8 Hz),
8.34 (d, 1H, H3, JHP = 7.2 Hz). 31P NMR (ꢁ60 °C): 2.90 (dd, J(109Ag–
P, 107Ag–P) = 362.5, 321.0 Hz).
3.4. Crystal structure determination
3.3. Synthesis of the complexes [Ag(CF3SO3)(PPh2{bzt})n]
X-ray data for compounds 1Ag, 2Ag and 3Ag ꢀ 0.5CH2Cl2 were
Complexes of general formula [Ag(CF3SO3)(PPh2{bzt})n] were
prepared from AgCF3SO3 (0.128 g, 0.5 mmol) in CH2Cl2, in the pres-
ence of an adequate quantity of benzo[1,2-b;4,3-b0]dithiophen-2-
diphenylphosphine (n = 1: 0.180 g, 0.49 mmol; n = 2: 0.374 g,
1.00 mmol; n = 3: 0.562 g, 1.5 mmol). The mixtures were stirred
overnight at room temperature, protected from light. After filtering
and reducing the solvent volume to ꢄ5 mL), the complexes were
recrystallized by slow diffusion of n-hexane, affording white crys-
talline products.
collected on a Bruker AXS APEX CCD area detector diffractometer at
150(2) K using graphite-monochromated Mo K
a (k = 0.71073 Å)
radiation. Intensity data were corrected for Lorentz polarization
effects. Empirical absorption correction using SADABS [18] was
applied and the data reduction was done with SMART and SAINT pro-
grams [19].
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SHELXL97 [22], all included in the package of programs WINGX-Version

244
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an electron count/cell of 143 which matches well with a n-hexane
or a dichloromethane molecule per asymmetric unit. Before SQUEEZE
R1 = 0.0801, afterwards R1 = 0.0764.
Acknowledgements
The authors thank to Fundação Para a Ciência e Tecnologia (FCT)
for financial support (POCTI/QUI/48443/2002). Pedro Florindo
thanks FCT for the Ph.D. grant conceded (SFRH/BD/12432/2003).
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Appendix A. Supplementary data
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[18] SADABS, Area-Detector Absorption Correction, Bruker AXS Inc., Madison, WI,
2004.
[19] SAINT: Area-Detector Integration Software (Version 7.23), Bruker AXS Inc.,
CCDC 122345 and 123454 contain the supplementary crystallo-
graphic data for 1Ag and 3Ag. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: de-
posit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at doi:10.1016/
j.poly.2008.11.013.
Madison, WI, 2004.
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