Coordination chemistry of 1,1′-bis(diphenylselenophosphoryl)ferrocene (dpspf) towards Group 11 elements. Crystal structures of [Ag(dpspf){(SPPh2)2CH2}]OTf and [Au(dpspf)][AuCl2]

Article abstract of DOI:10.1016/S0022-328X(00)00465-4

The ligand 1,1′-bis(diphenylselenophosphoryl)ferrocene, dpspf, reacted with various Group 11 derivatives to afford the complexes [M(dpspf)]X (M = Cu, Ag, Au; X = OTf, ClO₄, [AuCl₂]). The crystal structure of [Au(dpspf)][AuCl₂] revealed a trans coordination of the dpspf ligand and the presence of short Au-Au interactions in the cation. The complex [Ag(dpspf)]OTf can react further with bidentate ligands to give the four-coordinate complexes [M(dpspf)(L-L)]OTf (L-L = (SPPh₂)₂CH₂, (SePPh₂)₂CH₂, 2,2′-bipyridine or dpspf). The structure of the derivative with L-L = (SPPh₂)₂CH₂ was confirmed by X-ray diffraction.

Full text of DOI:10.1016/S0022-328X(00)00465-4

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 613 (2000) 50–55
Coordination chemistry of
1,1%-bis(diphenylselenophosphoryl)ferrocene (dpspf) towards Group
11 elements. Crystal structures of [Ag(dpspf){(SPPh2)2CH2}]OTf
and [Au(dpspf)][AuCl2]
Silvia Canales a, Olga Crespo a, M. Concepcio´n Gimeno a, Peter G. Jones b,
Antonio Laguna a,*
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC, 50009 Saragossa, Spain
b Institut fu¨r Anorganische und Analytische Chemie der Technischen Uni6ersita¨t, Postfach 3329, D-38023 Braunschweig, Germany
Received 25 April 2000; accepted 10 July 2000
Abstract
The ligand 1,1%-bis(diphenylselenophosphoryl)ferrocene, dpspf, reacted with various Group 11 derivatives to afford the
complexes [M(dpspf)]X (M=Cu, Ag, Au; X=OTf, ClO4, [AuCl2]). The crystal structure of [Au(dpspf)][AuCl2] revealed a trans
coordination of the dpspf ligand and the presence of short Au–Au interactions in the cation. The complex [Ag(dpspf)]OTf can
react further with bidentate ligands to give the four-coordinate complexes [M(dpspf)(LꢀL)]OTf (LꢀL=(SPPh2)2CH2,
(SePPh2)2CH2, 2,2%-bipyridine or dpspf). The structure of the derivative with LꢀL=(SPPh2)2CH2 was confirmed by X-ray
diffraction. © 2000 Elsevier Science B.V. All rights reserved.
Keywords: Trans coordination; Bidentate ligands; X-ray diffraction
1. Introduction
nium analogue, bis(diphenylselenophosphoryl)ferrocene
(dpspf), was similarly assigned as a trans-chelating lig-
and in the copper derivative [Cu(dpspf)]BF4, on the
basis of NMR spectroscopy [4] and it has been con-
firmed very recently, when this manuscript was in
preparation, in the silver analog [Ag(dpspf)]ClO4 [7].
The latter are the only known complexes of the Group
11 elements with the dpspf ligand. Here we report on
the coordination chemistry of dpspf with Cu(I), Ag(I),
Au(I) or Au(III) centres. Mono- and di-nuclear deriva-
tives are reported in which the selenium donor ligand
acts as bridging or chelating ligand and the metal
centres display linear or tetrahedral geometry.
The diphosphine 1,1%-bis(diphenylphosphine)ferro-
cene (dppf) has been widely exploited in coordination
chemistry during the last two decades [1]. It has a
strong bonding ability because of the two PPh2 groups
and it is a very flexible ligand that can modify its steric
bite in order to adapt to different geometric require-
ments of the metal centres. This has facilitated the
synthesis of a great number of mono- or poly-nuclear
gold or silver derivatives with different geometries [2,3].
The sulfuration product, bis(diphenylthiophospho-
ryl)ferrocene (dptpf), possesses a longer and more flex-
ible backbone and can thus function as a trans-
chelating ligand, as was confirmed recently in the spe-
cies [M(dptpf)]+ (MꢁCu [4], Ag, Au [5,6]). The sele-
2. Results and discussion
The reaction of dpspf with the derivatives
[Cu(NCMe)4]OTf, AgOTf or [Au(tht)2]ClO4 (OTf=
CF3SO3, tht=tetrahydrothiophene; molar ratio 1:1)
* Corresponding author. Tel.: +34-976-761185; fax: +34-976-
761187.
E-mail address: alaguna@posta.unizar.es (A. Laguna).
0022-328X/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00465-4

S. Canales et al. / Journal of Organometallic Chemistry 613 (2000) 50–55
51
Scheme 1. (i) [Cu(NCMe)4]OTf, AgOTf or [Au(tht)2]ClO4; (ii) 2 [AuCl(tht)]; (iii) 2 [Au(C6F5)3(OEt2)]; (iv) M=Ag, (SPPh2)2CH2, (SePPh2)2CH2,
bipy or dpspf (X=OTf).
(1)
gives the mononuclear complexes [M(dpspf)]X (X=
OTf, M=Cu, 1; Ag, 2 or X=ClO4, M=Au, 3) (see
Scheme 1). They are pale brown (1) or orange (2, 3) air-
and moisture-stable solids and behave as 1:1 elec-
trolytes in acetone solution. Their IR spectra show,
apart from the bands arising from the dpspf ligand,
The structure of complex 4 has been confirmed by an
X-ray crystal diffraction study. A selection of bond
those of the perchlorate at 1096(vs, br) and 625(m)
cm−1 or triflate at 1265(vs, br), 1225(s) and 1155(s)
lengths and angles are collected in Table 1. The asym-
cm−1. The positive-ion LSIMS exhibit a peak corre-
metric unit contains one and a half cations and one and
a half anions, with the gold atom of the half cation
lying on a twofold axis and that of the half anion on an
sponding to the cation [M(dpspf)]+ at m/z=776 (12%,
1), 821 (100%, 2) or 911 (35%, 3).
1
The H-NMR spectra show, apart from the multiplet
inversion centre. The extended structure involves three
from the phenyl protons, two multiplets for the a and b
[Au(dpspf)]+ cations connected through gold–gold in-
protons of the substituted cyclopentadienyl rings at
teractions (Fig. 1). The Au1···Au2 distance is short,
approximately 4.3 and 4.7 ppm. The 31P{1H}-NMR
,
3.0915(6) A, whereas the Au2···Au2c1 distance is
spectra at room temperature show a singlet at 33.0 (1),
34.9 (2) or 31.9 ppm (3). In complex 2 selenium satel-
lites are observed [J(PSe) 605 Hz].
,
much longer, 4.030 A; the angle Au2ꢀAu1ꢀAu2c1 is
The treatment of dpspf with [AuCl(tht)] in the molar
ratio 1:2 gives the ionic derivative [Au(dpspf)][AuCl2]
(4) as an orange solid. It behaves as a 1:1 electrolyte but
Table 1
a
its conductivity is lower than that of complex 3. The IR
spectra present a band at 335(m) cm−1 from w(AuꢀCl).
The positive-ion LSIMS exhibits a peak corresponding
to the cation [Au(dpspf)]+ [m/z=911(100%)]; the frag-
ment [Au2(dpspf)]+ [m/z=1106(15%)] is also present.
The 31P{1H}-NMR spectrum at room temperature
shows two singlets at 31.5 and 28.9 ppm; the second
one being slightly more intense. At lower temperature
(−55°C), the second peak (28.7 ppm) increases in
intensity and selenium satellites [J(PSe) 684 Hz] can be
observed. We surmise that this behavior is consistent
with an equilibrium between complex 4 and the dinu-
clear isomer [(m-dpspf)(AuCl)2] (Eq. (1)) that shifts to
the right at lower temperature.
,
Selected bond lengths (A) and angles (°) for compound 4
Au(1)ꢀSe(1)
Au(1)ꢀAu(2)
Au(2)ꢀSe(3)
Au(2)ꢀSe(2)
Se(1)ꢀP(1)
2.4217(8)
3.0915(6)
2.4000(9)
2.4050(9)
2.172(2)
Se(2)ꢀP(2)
Se(3)ꢀP(3)
Au(3)ꢀCl(1)
Au(3)ꢀCl(2)
Au(4)ꢀCl(3)
2.172(2)
2.176(3)
2.245(3)
2.250(3)
2.226(3)
Se(1)ꢀAu(1)ꢀSe(1)c1 178.14(5)
Se(2)ꢀAu(2)ꢀAu(1) 94.48(2)
Se(1)ꢀAu(1)ꢀAu(2)
86.72(3)
94.70(2)
P(1)ꢀSe(1)ꢀAu(1)
P(2)ꢀSe(2)ꢀAu(2)
P(3)ꢀSe(3)ꢀAu(2)
100.55(6)
98.81(7)
98.93(7)
Se(1)c1Au(1)ꢀAu(2)
Au(2)ꢀAu(1)ꢀAu(2)c1 81.36(2)
Se(3)ꢀAu(2)ꢀSe(2)
Se(3)ꢀAu(2)ꢀAu(1)
178.65(4)
86.60(3)
Cl(1)ꢀAu(3)ꢀCl(2) 179.19(11)
Cl(3)c2Au(4)ꢀCl(3)180.00
a Symmetry transformations used to generate equivalent atoms:
−x+1, y, −z+3/2, −x+1/2, −y+1/2, −z+1.

52
S. Canales et al. / Journal of Organometallic Chemistry 613 (2000) 50–55
The gold(III) complex [(m-dpspf){Au(C6F5)3}2] (5)
has been obtained by reaction of dpspf with
[Au(C6F5)3(OEt2)] in a 1:2 molar ratio. It is an orange,
air- and moisture-stable solid and is non-conducting in
acetone solutions. The mass spectrum shows the cation
molecular peak at m/z=2109 (25%).
1
The H-NMR spectrum shows three multiplets for
the phenyl and the a and b protons of the substituted
cyclopentadienyl rings. The 31P{1H}-NMR spectrum
presents only a singlet at 30.7 with selenium satellites
[J(PSe) 576 Hz]. The 19F-NMR spectrum shows six
resonances corresponding to the two types of pen-
tafluorophenyl groups, in a ratio 2:1.
Complex 2 can easily react further with other ligands,
increasing the coordination number of the silver atom.
Indeed, the reaction with bidentate ligands leads to the
four co-ordinate complexes [Ag(dpspf)(LꢀL)]OTf
[LꢀL=(SPPh2)2CH2 (6), (SePPh2)2CH2 (7), 2,2%-
bipyridine (bipy) (8) or dpspf (9)] (Scheme 1). They are
air- and moisture stable orange solids that behave as
1:1 electrolytes in acetone solutions. The positive-ion
LSIMS do not show the cation molecular peak,
[MꢀOTf]+, except for complex 7 [m/z=1363 (2%)].
The cation [Ag(dpspf)]+ is observed in all the com-
plexes [m/z=821 (55%)].
Fig. 1. The cation aggregate of compound 4 with the atom numbering
scheme. Hydrogen atoms have been omitted for clarity. Radii are
arbitrary.
Table 2
,
Selected bond lengths (A) and angles (°) for compound 6
AgꢀS(1)
AgꢀSe(1)
AgꢀS(2)
2.5919(12)
2.5936(6)
2.6012(11)
AgꢀSe(2)
Se(1)ꢀP(2)
Se(2)ꢀP(3)
2.6753(6)
2.1358(11)
2.1363(12)
The 31P{1H}-NMR spectrum presents only a singlet
for complex 8 (34.8 ppm) or 9 [33.5 ppm, J(PSe) 630
Hz], and two singlets for complex 6 or 7 corresponding
to the two different phosphorus of the two ligands. The
1H-NMR spectra are in agreement with the proposed
structures (see Section 3).
S(1)ꢀAgꢀSe(1)
S(1)ꢀAgꢀS(2)
Se(1)ꢀAgꢀS(2)
S(1)ꢀAgꢀSe(2)
127.82(3)
96.05(4)
110.93(3)
113.02(3)
Se(1)ꢀAgꢀSe(2)
S(2)ꢀAgꢀSe(2)
P(2)ꢀSe(1)ꢀAg
P(3)ꢀSe(2)ꢀAg
108.897(18)
93.75(3)
99.17(3)
109.74(3)
The structure of compound 6 has been established by
an X-ray diffraction study, although the precision was
somewhat limited by the presence of large amounts of
poorly defined solvent. Selected bond lengths and an-
gles are shown in Table 2. The silver atom displays a
distorted tetrahedral geometry (Fig. 2) with ligand bite
angles of 96.05(4) (S1ꢀAgꢀS2) and 108.897(18)°
(Se1ꢀAgꢀSe2). These bite angles are very dissimilar: the
first is similar to that found for the same ligand in the
81.36(2)°. This structural framework is different from
that in the related [Au(dptpf)]+ derivative [5], in which
,
loose dimers are formed (Au···Au 3.305, 3.370 A). The
coordination around the gold centres is linear
(Se1ꢀAu1ꢀSe1c178.14(5)°, Se3ꢀAu2ꢀSe2 178.65(4)°),
as in [Ag(dptpf)]ClO4 [7] (SeꢀAgꢀSe=176.5(1)°). The
almost ideal geometry shows the great flexibility of this
trans-bidentate chelating ligand. The AuꢀSe distances
,
(2.4000(9)–2.4217(8) A) compare well with those found
complex
[Ag{(SPPh2)2CH2}{(PPh2)2C2B10H10}]ClO4
,
in [Se{Au2(m-dppf)}] [8] (2.4055(11), 2.4218(11) A) and
(99.20(5)°) [12], whereas the second is much wider and
can be attributed to the greater flexibily of the dpspf
ligand, as is shown the synthesis of the trans-chelating
complexes. The AgꢀS bond lengths, 2.5916(15),
are longer than the values in [Se{Au(PPh3)}2] [9], which
contains a bridging selenide centre. The intramolecular
,
gold–iron contacts are 3.981 and 4.017 A. The corre-
sponding anions [AuCl2]−, which are not involved in
noteworthy contacts, exhibit linear geometries
(Cl1ꢀAu3ꢀCl2 179.19(11)°, Cl3c2ꢀAu4ꢀCl3 180° by
symmetry) and the AuꢀCl distances (2.226(3)–2.250(3)
,
2.6013(15) A, can be compared with the values found in
complexes such as [AgBr([18]-aneS6)] [11] ([18]-aneS6=
1,4,7,10,13,16-hexathiacyclooctadecane)
(2.514(1)–
,
2.636(1) A), [Ag{(SPPh2)2CH2}{(PPh2)2C2B10H10}]ClO4
,
A) are comparable to those obtained in other linear
,
(2.540(2), 2.588(2) A) [12] or [Ag2{S2C2(CN)2}(PPh3)4]
gold derivatives such as [(m-dppf)(AuCl)2] (three crys-
,
[13] (2.568(7), 2.653(7) A) for the silver atom in a
tetrahedral geometry. Nevertheless, they are slightly
,
talline modifications, AuꢀCl 2.2815(13)–2.300(3) A)
[3,10]. The cyclopentadienyl rings are staggered by
17.9° around the Cp···Cp axis (Cp=centre of the cy-
clopentadienyl ring) as defined by the torsion angle
C(31)ꢀCpꢀCpꢀC(37).
longer than in the compound [Ag2(m-dptpf){(SPPh2)2-
,
CH2}2]ClO4 [6] (2.514(2)–2.434(2) A). The AgꢀSe dis-
,
tances (2.5936(6), 2.6753(6) A) are similar to those
found in [Ag{MeSe(CH2)2SeMe}2]+ (2.626(2)–2.638(1)

S. Canales et al. / Journal of Organometallic Chemistry 613 (2000) 50–55
53
+
,
A) [14] or in [AgL2] (L=1,5-diselenacyclooctane)
3.1. Syntheses
,
(2.636(4)–2.695(4) A) [15]. This structure is also differ-
ent from that of the complex [Ag2(m-dptpf{(SPPh2)2-
CH2}2]ClO4 which arose from the reaction of
[Ag(dptpf)]ClO4 and (SPPh2)2CH2, in a molar relation
1:1, and consists of a polymeric chain [6]. The cyclopen-
tadienyl rings are staggered by 21.4° around the
Cp···Cp axis as defined by the torsion angle
C(1)ꢀCpꢀCpꢀC(7).
3.1.1. [Cu(dpspf )]OTf (1)
To a solution of dpspf (0.071 g, 0.1 mmol) in tetrahy-
drofurane under argon atmosphere (20 cm3) was added
[Cu(NCMe)4]OTf (0.037 g, 0.1 mmol) and the mixture
stirred for 30 min. Concentration of the solution to
approximately 5 cm3 and addition of diethyl ether (10
cm3) gave complex 1 as a pale brown solid. Yield 70%.
\
110 V−1 cm2 mol−1. Anal Found (%): C, 45.09; H,
M
3.43; S, 3.89. Calc. for C35H28CuF3FeO3P2SSe2: C,
1
3. Experimental
45.40; H, 3.03; S, 3.46. H-NMR, l: 4.33 (m, 4H), 4.71
(m, 4H), 7.3–7.8 (m, 20H, Ph). 31P{1H}-NMR, l: 33.0
Infrared spectra were recorded on a Perkin–Elmer
(s).
883 spectrophotometer, over the range 4000–200 cm−1
,
using Nujol mulls between polyethylene sheets. Con-
ductivities were measured in approximately 5×10−4
mol dm−3 solutions with a Philips 9509 conductimeter.
C, H, N and S analyses were carried out with a
Perkin–Elmer 2400 microanalyser. Mass spectra were
recorded on a VG Autospec, with the liquid secondary-
ion mass spectra (LSIMS) technique, using nitrobenzyl
3.1.2. [Ag(dpspf )]OTf (2)
To a solution of dpspf (0.071 g, 0.1 mmol) in
dichloromethane (20 cm3) was added AgOTf (0.026 g,
0.1 mmol) and the mixture stirred for 30 min. Concen-
tration of the solution to approximately 5 cm3 and
addition of diethyl ether (10 cm3) gave complex 2 as an
orange solid. Yield 50%. \M 67 V−1 cm2 mol−1. Anal.
Found (%): C, 42.98; H, 2.90; S, 3.85. Calc. for
C35H28AgF3FeO3P2SSe2: C, 43.34; H, 2.89; S, 3.30.
1H-NMR, l: 4.27 (m, 4H), 4.68 (m, 4H), 7.3–7.9 (m,
20H, Ph). 31P{1H}-NMR, l: 34.9 [s, J(SeP) 605 Hz].
1
alcohol as matrix. H-, 19F- and 31P{1H}-NMR spectra
were recorded on a Varian UNITY 300, Bruker
ARX·300 or GEMINI 2000 apparatus in CDCl3 solu-
tions (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).
3.1.3. [Au(dpspf )]X (X=ClO4, 3; [AuCl2], 4)
To a solution of dpspf (0.071 g, 0.1 mmol) in
dichloromethane (20 cm3) was added [Au(tht)2]ClO4
(0.047 g, 0.1 mmol) or [AuCl(tht)] (0.064 g, 0.2 mmol)
and the mixture stirred for 30 min. Concentration of
the solution to approximately 5 cm3 and addition of
diethyl ether (10 cm3) gave complexes 3 or 4 as orange
The starting materials [AuCl(tht)] [16], [Au(tht)2]ClO4
[17], [Au(C6F5)3(OEt2)] [18], [Cu(NCMe)4]OTf [19], dp-
spf [5], (SPPh2)2CH2 [20] and (SePPh2)2CH2 [20] were
prepared by published procedures. CAUTION: per-
chlorate salts with organic cations may be explosive.
solids. Complex 3: yield 60%. \M 147 V−1 cm2 mol−1
.
Anal. Found (%): C, 40.10; H, 2.40. Calc. for
1
C34H28AuClFeO4P2Se2: C, 40.47; H, 2.77. H-NMR, l:
4.39 (m, 4H), 4.65 (m, 4H), 7.4–7.8 (m, 20H, Ph).
31P{1H}-NMR, l: 31.9 (s). Complex 4: yield 76%. \M
106 V−1 cm2 mol−1. Anal. Found (%): C, 34.19; H,
2.62. Calc. for C34H28Au2Cl2FeP2Se2: C, 34.66; H, 2.38.
1H-NMR, l: (r.t.) 4.65 (m, 4H), 4.75 (m, 4H), 7.4–7.8
(m, 20H, Ph); (−55°C) 4.60 (m, 4H), 4.70 (m, 4H),
7.4–7.8 (m, 20H, Ph). 31P{1H}-NMR, l: (r.t.) 28.9 (s),
31.5 (s); (−55°C) 28.7 [s, J(SeP) 684 Hz], 30.3 (s).
3.1.4. [(v-dpspf ){Au(C6F5)3}2] (5)
To a solution of [Au(C6F5)3(OEt2)] (0.154 g, 0.2
mmol) in dichloromethane (20 cm3) was added dpspf
(0.071 g, 0.1 mmol) and the mixture stirred for 30 min.
Concentration of the solution to approximately 5 cm3
and addition of hexane (10 cm3) gave complex 5 as an
orange solid. Yield 73%. \M 7 V−1 cm2 mol−1. Anal.
Found (%): C, 39.80; H, 2.22. Calc. for
Fig. 2. The cation of compound 6 with the atom numbering scheme.
Hydrogen atoms have been omitted for clarity. Radii are arbitrary.
1
C70H28Au2F30FeP2Se2: C, 39.84; H, 1.40. H-NMR, l:

54
S. Canales et al. / Journal of Organometallic Chemistry 613 (2000) 50–55
Table 3
6.89. Calc. for C60H50AgF3FeO3P4S3Se2: C, 50.81; H,
3.52; S, 6.77. H-NMR, l: 4.40 (m, 4H), 4.54 (m, 4H),
Details of data collection and structure refinement for complexes 4
and 6
1
4.14 (t, 2H, J(PH)=13 Hz), 7.3–8 (m, 40H, Ph).
31P{1H}-NMR, l: 37.3 (s, 2P, dpspf), 32.5 [s, 2P,
(SPPh2)2CH2]. Complex 7: yield 74%. \M 139 V−1 cm2
mol−1. Anal. Found (%): C, 47.3; H, 3.51; S, 2.54.
Calc. for C60H50AgF3FeO3P4SSe4: C, 47.65; H, 3.31; S,
Compound
Empirical formula
4 5/3 CH2Cl2
C35.67H31.33Au2-
Cl5.33FeP2Se2
Yellow prism
0.26×0.13×0.08
Monoclinic
C2/c
29.615(3)
17.6644(18)
23.448(2)
90
106.537(3)
90
11759(2)
12
2.235
1318.65
6·3CH2Cl2
C63H56AgCl6F3FeO3-
P4S3Se2
Yellow prism
0.41×0.28×0.12
Triclinic
Crystal habit
Crystal size (mm−1
Crystal system
Space group
)
1
2.12. H-NMR, l: 4.41 (m, 4H), 4.48 (m, 6H, C5H4+
CH2), 7.4–7.8 (m, 40H, Ph). 31P{1H}-NMR, l: 26.3 [s,
2P, (SePPh2)2CH2], 32.2 (s, 2P, dpspf). Complex 8: yield
64%. \M 120 V−1 cm2 mol−1. Anal. Found (%): C,
47.58; H, 3.24; S, 3.04; N, 2.20. Calc. for
C45H36AgF3FeN2O3P2SSe2: C, 48.0; H, 3.20; S, 2.84; N,
(
P1
,
a (A)
14.2813(12)
16.3269(14)
16.5422(14)
63.307(3)
84.146(3)
81.568(3)
3406.0(5)
2
,
b (A)
,
c (A)
a (°)
i (°)
k (°)
1
2.48. H-NMR, l: 4.31 (m, 4H), 4.69 (m, 4H), 7.5–7.7
3
,
U (A )
Z
(m, 20H, Ph), 8.64 (m, 1H, bipy), 8.37 [d, 1H, bipy,
J(HH) 7.8 Hz], 7.94 [t, 1H, bipy, J(HH) 6.2 Hz], 7.40
(m, 1H, bipy). 31P{1H}-NMR, l: 34.8 (s). Complex 9:
yield 51%. \M 147 V−1 cm2 mol−1. Anal. Found (%):
Dcalc (g cm−3
M
)
1.631
1672.48
1672
−130
57
2.04
0.488, 0.792
67140
F(000)
T (°C)
2qmax (°)
7416
−130
53
10.16
C,
48.96;
H,
3.23;
S,
2.07.
Calc.
for
C69H56AgF3Fe2O3P4SSe4: C, 49.25; H, 3.33; S, 1.90.
1H-NMR, l: 4.36 (m, 8H), 4.62 (m, 8H), 7.4–7.8 (m,
40H, Ph). 31P{1H}-NMR, l: 33.5 [s, J(SeP) 630 Hz].
v(Mo–Ka) (mm−1
)
Transmission
Reflections measured 67080
0.745, 0.928
Unique reflections
16866
0.1051
0.0529
0.1584
16876
0.0518
0.0574
0.1929
3.2. Crystallography
Rint
a
R
(F\4|(F))
wR2 b(F2, all
reflections)
The crystals were mounted in inert oil on a glass fibre
and transferred to the cold gas stream of a Bruker
SMART 1000 CCD area detector equipped with an
LT-3 low temperature attachment. Absorption correc-
tions were based on multiple scans (program SADABS).
Crystallographic data are summarised in Table 3.
Structures were solved by direct methods and refined
against F2 (program SHELXL-97, G.M. Sheldrick, Uni-
versity of Go¨ttingen, Germany).
Reflections used
Parameters
16866
787
620
1.052
3.299
16876
767
199
0.756
3.399
Restraints
c
S
−3
,
Max. Dz (e A
)
a R(F)=(F)=ꢀꢁꢁFoꢁ−ꢁFcꢁꢁ/ꢀꢁFoꢁ.
b wR(F2)=[ꢀ{w(F2o−F2c)2}/{w(F2o)2}]1/2
;
w
−1=|2(F2o)+(aP)2+
bP, where P=[F2o+2F2c]/3 and a and b are constants adjusted by the
program.
c S=[ꢀ{w(Fo2−Fc2)2}/(n−p)]0.5, where n is the number of data and
p the number of parameters.
3.2.1. Special refinement details
The asymmetric unit of compound 4 contains four
dichloromethane sites, three of which are disordered
(half occupied). The overall stoichiometry is thus one
formula unit of the complex to 5/3 molecules of
dichloromethane. The ring C72–C76 is disordered over
two positions. All rings were refined isotropically with
idealised geometry. The poor R values obtained for
compound 6 are associated with the ill-defined or disor-
dered solvent and anion; an extensive system of re-
straints to light atom temperature factors and local ring
symmetry was employed to improve refinement
stability.
4.40 (m, 4H), 4.68 (m, 4H), 7.3–7.9 (m, 20H, Ph).
31P{1H}-NMR, l: 30.7 [s, J(SeP) 576 Hz]. 19F-NMR,
l: −119.7 (m, 4F, o-F), −157.5 [t, 2F, p-F, J(FF)
20.1 Hz], −161.3 (m, 4F, m-F); −122.5 (m, 2F, o-F),
−157.4 [t, 1F, p-F, J(FF) 20.2 Hz], −161.4 (m, 2F,
m-F).
3.1.5. [Ag(dpspf )(LꢀL)]OTf [LꢀL=(SPPh2)2CH2, 6;
(SePPh2)2CH2, 7; bipy, 8; dpspf, 9]
To a solution of [Ag(dpspf)]OTf (0.097 g, 0.1 mmol)
in dichloromethane (20 cm3) was added (SPPh2)2CH2
(0.045 g, 0.1 mmol), (SePPh2)2CH2 (0.054 g, 0.1 mmol),
bipy (0.015 g, 0.1 mmol) or dpspf (0.071 g, 0.1 mmol),
respectively and the mixture stirred for 30 min. Concen-
tration of the solution to approximately 5 cm3 and
addition of diethyl ether (10 cm3) gave complexes 6–9
as orange solids. Complex 6: yield 63%. \M 117 V−1
cm2 mol−1. Anal. Found (%): C, 50.80; H, 3.54; S,
4. Supplementary material
Complete crystallographic data (excluding structure
factors) have been deposited at the Cambridge Crystal-
lographic Data Centre under the CCDC nos. 143 500
(4) and 143 501 (6). Copies can be obtained free of

S. Canales et al. / Journal of Organometallic Chemistry 613 (2000) 50–55
55
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Acknowledgements
We thank the Direccio´n General de Ensen˜anza Supe-
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