1,1′-Bis(diphenylthiophosphoryl)ferrocene complexes of gold(I) and gold(III)

Article abstract of DOI:10.1016/S0022-328X(99)00527-6

Linear and three-coordinate gold(I) complexes with the ferrocenyl derivative 1,1′-bis(diphenylthiophosphoryl)ferrocene (dptpf) of the type [(μ-dptpf)(AuX)₂] (X = Cl, 1; C₆F₅), [(μ-dptpf)(AuPPh₃)₂](ClO

Full text of DOI:10.1016/S0022-328X(99)00527-6

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 596 (2000) 10–15
1,1%-Bis(diphenylthiophosphoryl)ferrocene complexes of gold(I) and
gold(III)
M. Concepcio´n Gimeno a, Peter G. Jones b, Antonio Laguna a,*, Cristina Sarroca a
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, Technische Uni6ersita¨t Braunschweig, Postfach 3329, D-38023 Braunschweig, Germany
Received 18 June 1999
Abstract
Linear and three-coordinate gold(I) complexes with the ferrocenyl derivative 1,1%-bis(diphenylthiophosphoryl)ferrocene (dptpf)
of the type [(m-dptpf)(AuX)2] (X=Cl, 1; C6F5), [(m-dptpf)(AuPPh3)2](ClO4)2 or [Au(dptpf)(PPh3)]ClO4 have been obtained.
Oxidation of 1 with chlorine gave the mixed gold(I)–gold(III) compound [Au(dptpf)][AuCl4]. The dinuclear gold(III) complexes
[(m-dptpf){Au(C6F5)3}2] or [(m-dptpf){Au(C6F5)2Cl}2] were obtained from the corresponding gold precursors and dptpf. The
crystal structures of [Au(dptpf)][AuCl4] and [(m-dptpf){Au(C6F5)2Cl}2] have been determined by X-ray diffraction studies. © 2000
Elsevier Science S.A. All rights reserved.
Keywords: Gold; Ferrocene; Bis(diphenylthiophosphoryl)ferrocene
the formation of the species [M(dptpf)]+ (M=Cu, Ag,
1. Introduction
Au) with dptpf acting as a trans-chelating ligand
[11,12]. Here we report on the coordination chemistry
of dptpf with gold-(I) and -(III) centres. Mono- and
di-nuclear derivatives are reported in which the S-donor
ligand acts as bridging or chelating ligand.
Recently, the chemistry of ferrocene-containing com-
plexes has received much attention associated with their
increasing applications in organic synthesis, production
of fine chemicals, homogeneous catalysis, and materials
science [1–4]. Ferrocene has become a versatile building
block for the synthesis of compounds with tailor-made
properties, and numerous derivatives have been re-
ported in which the cyclopentadienyl rings are bound to
organic groups containing one or more donor atoms
[1]. A good example is the diphosphine 1,1%-bis(-
diphenylphosphine)ferrocene (dppf); it is a very flexible
ligand that can modify its steric bite in order to adapt
to different geometric requirements of the metal cen-
tres. This has facilitated the synthesis of a great number
of mononuclear (with trigonal planar or tetrahedral
geometry) or polynuclear gold or silver derivatives [5–
10].
2. Results and discussion
The reaction of dptpf with the gold complexes
[AuX(tht)] (tht=tetrahydrothiophene; molar ratio 1:2)
gives the dinuclear complexes [(m-dptpf)(AuX)2] (X=
Cl, 1; C6F5, 2) (see Scheme 1). They are yellow air- and
moisture-stable solids and are non-conducting in ace-
tone solutions. Their IR spectra show the vibration
w(AuꢀCl) at 341(m) cm−1 (1) and the bands arising
from the pentafluorophenyl group at 1502(vs), 959(vs)
and 796(m) cm−1 (2). The positive liquid secondary ion
mass spectra (LSIMS) do not show the cation molecu-
lar peak; however, the cation [Au(dptpf)]+ appears at
m/z=815 (1, 100; 2, 13%).
The sulfuration product of the diphosphine, bis-
(diphenylthiophosphoryl)ferrocene (dptpf), is a ligand
with a longer and more flexible backbone that permits
1
The H-NMR spectra show two multiplets for the a
and b protons of the substituted cyclopentadienyl
groups. The 19F-NMR spectrum of 2 presents three
resonances for the ortho-, meta- and para-fluorines of
* Corresponding author. Tel.: +34-97-676-1185; fax: +34-97-676-
1187.
E-mail address: alaguna@posta.unizar.es (A. Laguna)
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00527-6

M.C. Gimeno et al. / Journal of Organometallic Chemistry 596 (2000) 10–15
11
Scheme 1. (i) 2[AuX(tht)]; (ii) 2[Au(OClO3)(PPh3)]; (iii) [Au(OClO3)(PPh3)]; (iv) Cl2; (v) 2[Au(C6F5)3(OEt2)]; (vi) [Au(C6F5)2Cl]2.
the C6F5 group. The 31P-{1H}-NMR spectra at room
temperature show a singlet for 1 and a multiplet for 2,
due to the coupling with the fluorine atoms.
ionic complex [Au(dptpf)][AuCl4] (5) is isolated. We
believe that the intermediate orange–red product
should be the dinuclear gold(II) derivative, [(m-
dptpf)(AuCl2)2], but that it isomerises to the mixed
gold(I)–gold(III) derivative. Complex 5 behaves as a
1:1 electrolyte in acetone solution. In the IR spectrum
the w(AuꢀCl) vibration appears at 359(m) cm−1. The
31P-{1H}-NMR spectrum presents a singlet at 45.7
ppm.
The structure of complex 5 has been confirmed by an
X-ray crystal diffraction study (Fig. 1, Table 1). The
asymmetric unit consists of one cation on a general
position and two half anions, in each of which the gold
and two chlorine atoms lie on a two-fold axis. In the
cation the gold atom is linearly coordinated with an
angle SꢀAuꢀS of 174.5(2)°, which is marginally more
bent than in the complex [Au(dptpf)]OTf (176.43(12)
The treatment of dptpf with [Au(OClO3)(PPh3)] in
the molar ratio 1:2 or 1:1 gives the dinuclear [(m-
dptpf)(AuPPh3)2](ClO4)2 (3) or the mononuclear [Au-
(dptpf)(PPh3)]ClO4 (4a), respectively. The complex
[Au(dptpf)(PPh3)]OTf (4b) (OTf=CF3SO3) can be ob-
tained by reaction of [Au(dptpf)]OTf with PPh3. These
are yellow–brown air- and moisture-stable solids and
behave as 1:2 (3) or 1:1 (4a, 4b) electrolytes in acetone
solution. Their IR spectrum shows, apart from the
bands arising from the dptpf and phosphine ligands,
those of the perchlorate at 1096(vs, br) and 623(m)
cm−1 or triflate at 1265(vs, br), 1225(s) and 1155(s)
cm−1. The positive-ion LSIMS exhibit a peak corre-
sponding to the cation [Au2(dptpf)(PPh3)]+ [m/z=1273
(19%)] for complex 3 and the cation molecular peak
[Au(dptpf)(PPh3)]+ [m/z=1077, 20%)] for complexes
4a and 4b. The most intense peak in these spectra is the
fragment [Au(dptpf)]+, which appears at m/z=815.
1
The H-NMR spectra show, apart from the multiplet
from the phenyl protons, two multiplets of the cy-
clopentadienyl ring. The 31P-{1H}-NMR spectra
present two singlets at 41.7 and 37.4 ppm (3) or 45.1
and 37.6 ppm (4), for the two different phosphorus
environments.
The oxidative addition of chlorine to dinuclear
gold(I) derivatives is a standard synthesis of dinuclear
gold(II) complexes with gold–gold bonds. We therefore
studied the reaction of complex 1 with an equimolar
amount of chlorine. The yellow solution of 1 in
dichloromethane turns orange–red on addition of the
halogen, but the solution slowly fades to yellow and the
Fig. 1. Molecular structure of the cation of complex 5 in the crystal
showing the atom numbering scheme. Hydrogen atoms are omitted
for clarity.

12
M.C. Gimeno et al. / Journal of Organometallic Chemistry 596 (2000) 10–15
Table 1
two PꢁS bonds are gauche to each other, with the
a
,
Selected bond lengths (A) and angles (°) for complex 5
torsion angle P1ꢀS1···S2ꢀP2 −41.9(4)°. Noteworthy
features of the crystal packing are several interactions
of the form CꢀH···Cl with H···Cl between 2.64 and 3.05
Bond lengths
Au(1)ꢀS(1)
FeꢀC(15)
FeꢀC(11)
FeꢀC(21)
FeꢀC(12)
FeꢀC(23)
P(1)ꢀC(11)
P(1)ꢀC(31)
P(2)ꢀC(61)
P(2)ꢀC(51)
Au(2)ꢀCl(3)
Au(2)ꢀCl(2)
Au(3)ꢀCl(4)
2.281(5)
Au(1)ꢀS(2)
2.299(5)
2.014(12) FeꢀC(25)
2.025(12) FeꢀC(14)
2.031(12) FeꢀC(24)
2.049(12) FeꢀC(22)
2.052(13) FeꢀC(13)
1.780(10) P(1)ꢀC(41)
1.804(10) P(1)ꢀS(1)
1.800(9)
1.826(10) P(2)ꢀS(2)
2.271(9)
2.280(8)
2.278(6)
2.022(12)
2.031(12)
2.035(12)
2.049(13)
2.052(13)
1.804(10)
2.023(7)
1.813(10)
1.986(7)
2.280(6)
2.272(11)
2.287(9)
,
A; the shortest is H62···Cl6 (x, −1+y, z), with a
CꢀH···Cl angle of 165°. These contacts can reasonably
be assigned as hydrogen bonds [13,14].
The cyclopentadienyl rings adopt an almost eclipsed
orientation with a torsion angle C(12)–centre–centre–
C(21) of 10.1°. The intramolecular gold–iron contact is
P(2)ꢀC(21)
,
3.869 A, but there are no short gold–gold interactions,
,
the shortest Au···Au distance being 4.75 A.
Au(2)ꢀCl(1)
Au(3)ꢀCl(5)
Au(3)ꢀCl(6)
The gold(III) complexes [(m-dptpf){Au(C6F5)3}2] (6)
or [(m-dptpf){Au(C6F5)2Cl}2] (7) have been obtained by
reaction of dptpf with [Au(C6F5)2Cl]2 or [Au(C6F5)3-
(OEt2)], respectively, in a 1:2 molar ratio. They are
orange (6) or yellow (7) air- and moisture-stable solids
and are non-conducting in acetone solutions. In the IR
spectrum of 6 the w(AuꢀCl) vibration appears at 349(m)
cm−1. The positive-ion LSIMS do not show the cation
molecular peak; however the fragments [Au(C6F5)3-
(dptpf)]+ [m/z=1316, 3%)] or [Au(C6F5)2ClH(dptpf)]+
[m/z=1185, 1%)] and [Au(C6F5)2(dptpf)]+ [m/z=
1149, 40%)] are present for complexes 6 or 7, respec-
tively.
Bond angles
S(1)ꢀAu(1)ꢀS(2)
C(61)ꢀP(2)ꢀC(21)
C(21)ꢀP(2)ꢀC(51)
C(21)ꢀP(2)ꢀS(2)
P(2)ꢀS(2)ꢀAu(1)
C(12)ꢀC(11)ꢀP(1)
C(22)ꢀC(21)ꢀP(2)
C(36)ꢀC(31)ꢀP(1)
C(46)ꢀC(41)ꢀP(1)
C(56)ꢀC(51)ꢀP(2)
C(66)ꢀC(61)ꢀP(2)
174.5(2)
107.0(6)
111.4(6)
110.2(5)
97.5(2)
125.4(8)
126.4(8)
121.1(8)
119.6(8)
119.5(7)
123.2(7)
P(1)ꢀS(1)ꢀAu(1)
103.6(3)
C(61)ꢀP(2)ꢀC(51) 106.6(6)
C(61)ꢀP(2)ꢀS(2)
C(51)ꢀP(2)ꢀS(2)
107.8(5)
113.4(5)
C(15)ꢀC(11)ꢀP(1) 125.3(8)
C(25)ꢀC(21)ꢀP(2) 125.5(8)
C(32)ꢀC(31)ꢀP(1) 118.7(8)
C(42)ꢀC(41)ꢀP(1) 120.3(8)
C(52)ꢀC(51)ꢀP(2) 120.3(7)
C(62)ꢀC(61)ꢀP(2) 116.8(7)
Cl(3)ꢀAu(2)ꢀCl(1)
90.3(2)
Cl(1)c1ꢀAu(2)ꢀCl(1) 179.5(3)
Cl(1)ꢀAu(2)ꢀCl(2) 89.7(2)
Cl(4)ꢀAu(3)ꢀCl(4)c2 179.7(4)
Cl(4)ꢀAu(3)ꢀCl(6) 90.1(2)
Cl(3)ꢀAu(2)ꢀCl(2) 180.0
1
Cl(5)ꢀAu(3)ꢀCl(4)
89.9(2)
The H-NMR spectra show two multiplets for the a
Cl(5)ꢀAu(3)ꢀCl(6) 180.0
and b protons of the cyclopentadienyl ring, and the
31P-{1H}-NMR spectra present only a singlet. The 19F-
NMR spectra show six resonances corresponding to
two types of pentafluorophenyl groups, in a ratio 1:1 (7,
indicating a cis position for the two C6F5 groups) or 2:1
(6), due to the ortho, meta or para fluorine atoms.
The crystal structure of complex 7 has been estab-
lished by an X-ray diffraction study (Fig. 2). A selec-
tion of bond lengths and angles are presented in Table
2. The iron atom lies on a two-fold axis and thus only
half of the molecule corresponds to the asymmetric
unit. The geometry of the gold atoms is square-planar
with the two pentafluorophenyl groups occupying cis
a Symmetry transformations used to generate equivalent atoms:
(c1) −x, −x+y, −z−1/3; (c2) y, x, −z.
,
positions; the gold atom lies 0.021 A out of the plane of
Table 2
,
Selected bond lengths (A) and angles (°) for complex 7
Bond lengths
AuꢀC(41)
AuꢀC(51)
AuꢀCl(1)
AuꢀS
2.008(8)
2.040(8)
2.316(2)
2.386(2)
SꢀP
2.020(3)
1.775(8)
1.805(9)
1.816(8)
PꢀC(11)
PꢀC(31)
PꢀC(21)
Fig. 2. The structure of complex 7 in the crystal with the atom
Bond angles
C(41)ꢀAuꢀC(51)
C(41)ꢀAuꢀCl(1)
C(51)ꢀAuꢀCl(1)
C(41)ꢀAuꢀS
C(51)ꢀAuꢀS
Cl(1)ꢀAuꢀS
labelling scheme.
87.9(3)
174.6(2)
87.4(2)
C(11)ꢀPꢀC(31)
C(11)ꢀPꢀC(21)
C(31)ꢀPꢀC(21)
C(11)ꢀPꢀS
C(31)ꢀPꢀS
C(21)ꢀPꢀS
106.2(4)
107.9(3)
106.9(3)
115.7(3)
106.8(3)
112.7(3)
and 178.26(11), two independent molecules) [6]. The
AuꢀS bond distances are 2.281(5) and 2.299(5) A,
which are also in the same range as those in [Au-
(dptpf)]OTf (2.280(3)–2.302(3) A). The coordination of
the gold(III) atoms is square-planar as expected. The
,
93.9(2)
174.4(2)
90.53(7)
108.08(10)
,
PꢀSꢀAu

M.C. Gimeno et al. / Journal of Organometallic Chemistry 596 (2000) 10–15
13
1
,
the four donor atoms. The AuꢀS distance is 2.386(2) A
and is of the same order as those in similar complexes
such as [Au(C6F5)2{(SPPh2)2CCH2Cp}] (2.3552(9) and
C46H28Au2F10FeP2S2: C, 41.05; H, 2.1; S, 4.75%. H-
NMR, l: 4.65 (m, 4H), 4.70 (m, 4H), 7.4–7.7 (m, 20H,
Ph). 31P-{1H}-NMR, l: 46.7 (m). 19F-NMR, l:
−116.7 (m, 2F, o-F), −160.3 (t, 1F, p-F, J(FF) 19.3
Hz), −163.3 (m, 2F, m-F).
,
,
2.3626(9) A) [15]. The AuꢀCl distance is 2.316(2) A,
similar to those in complexes such as [AuCl2(h2-S2CCl)]
[16], but longer than those in [AuCl4]− salts (e.g.
,
2.281(3)–2.287(2) A) [17], presumably because of the
higher trans influence of the pentafluorophenyl group.
3.1.2. [(v-dptpf)(AuPPh3)2](ClO4)2 (3) or
[Au(dptpf)(PPh3)]ClO4 (4a)
,
The gold–iron distance is 4.821 A, longer than in
complex 5. The shortest Cl···H and F···H contacts are
C36ꢀH36···Cl1 (1−x, 1−y, 1−z; H···Cl 2.65 A, angle
149°) and C23ꢀH23···F2 (x, 1−y, 0.5+z; H···F 2.55
To a solution of [Au(OClO3)(PPh3)] (0.2 or 0.1
mmol, respectively) in dichloromethane (20 cm3) was
added dptpf (0.062 g, 0.1 mmol) and the mixture was
stirred for 90 min. Concentration of the solution to ca.
5 cm3 and addition of diethyl ether (10 cm3) gave
complexes 3 and 4a as yellow–brown solids. Complex
3: yield 88%. \M 200 ohm−1 cm2 mol−1. Elemental
analysis (%), Found: C, 48.1; H, 3.3; S, 4.15. Calc. for
C70H58Au2Cl2FeO8P4S2: C, 48.45; H, 3.35; S, 3.7%.
1H-NMR, l: 4.59 (m, 4H), 4.71 (m, 4H), 7.3–7.78 (m,
50H, Ph). 31P-{1H}-NMR, l: 37.4 (s, PPh3), 47.1 (s,
dptpf). Complex 4a: yield 62%. \M 135 ohm−1 cm2
mol−1. Elemental analysis (%), Found: C, 52.8; H,
2.35; S, 5.19. Calc. for C52H43AuClFeO4P3S2: C, 53.0;
,
,
A, angle 168°).
3. Experimental
IR spectra were recorded on a Perkin–Elmer 883
spectrophotometer, over the range 4000–200 cm−1
,
using Nujol mulls between polyethylene sheets. Con-
ductivities were measured in ca. 5×10−4 mol dm−3
solutions with a Philips 9509 conductimeter. C, H, and
S analyses were carried out with a Perkin–Elmer 2400
microanalyser. Mass spectra were recorded on a VG
Autospec, with the LSIMS technique, using nitrobenzyl
alcohol as matrix. 1H-, 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).
The starting materials [AuCl(tht)] [18], [Au(C6F5)-
(tht)] [18], [Au(C6F5)3(OEt2)] [18], [Au(C6F5)2Cl]2 [19],
and dptpf [20] were prepared by published procedures.
[Au(OClO3)(PPh3)] was prepared from [AuCl(PPh3)]
[18] by reaction with AgClO4 in dichloromethane. All
other chemicals used were commercially available and
used without further purification. Caution: perchlorate
salts with organic cations may be explosive.
1
H, 2.4; S, 5.45%. H-NMR, l: 4.49 (m, 4H), 4.58 (m,
4H), 7.3–7.78 (m, 35H, Ph). 31P-{1H}-NMR, l: 37.6 (s,
PPh3), 45.1 (s, dptpf).
3.1.3. [Au(dptpf)(PPh3)]OTf (4b)
To a solution of [Au(dptpf)]OTf (0.092 g, 0.1 mmol)
in 20 cm3 of dichloromethane was added PPh3 (0.026 g,
0.1 mmol) and the mixture was stirred for 10 min.
Concentration of the solution to ca. 5 cm3 and addition
of diethyl ether (10 cm3) gave complex 4b as a yellow–
brown solid. Yield 77%. \M 149 ohm−1 cm2 mol−1
.
Elemental analysis (%), Found: C, 50.95; H, 3.85; S,
4.85. Calc. for C53H43AuF3FeO3P3S3: C, 50.45; H, 3.6;
S, 5.05%.
3.1.4. [Au(dptpf)][AuCl4] (5)
To a solution of complex 1 (0.108 g, 0.1 mmol) in 30
cm3 of dichloromethane was added a CCl4 solution of
chlorine (0.25 cm3, 0.4 N, 0.1 mmol) and the mixture
was stirred for 10 min. Concentration of the solution to
ca. 5 cm3 and addition of diethyl ether (10 cm3) gave
complex 5 as a yellow solid. Yield 87%. \M 139 ohm−1
cm2 mol−1. Elemental analysis (%), Found: C, 35.8; H,
2.55; S, 4.85. Calc. for C34H28Au2Cl4FeP2S2: C, 35.3; H,
3.1. Syntheses
3.1.1. [(v-dptpf)(AuX)2] (X=Cl, 1; C6F5, 2)
To a solution of dptpf (0.062 g, 0.1 mmol) in
dichloromethane (20 cm3) was added [AuCl(tht)] (0.064
g, 0.2 mmol) or [Au(C6F5)(tht)] (0.090 g, 0.2 mmol) and
the mixture was stirred for 90 min. Concentration of
the solution to ca. 5 cm3 and addition of diethyl ether
(10 cm3) gave complexes 1 or 2 as yellow solids. Com-
plex 1: yield 82%. \M 13 ohm−1 cm2 mol−1. Elemental
analysis (%), Found: C, 38.05; H, 2.6; S, 5.5. Calc. for
C34H28Au2Cl2FeP2S2: C, 37.65; H, 2.6; S, 5.9%. 1H-
NMR, l: 4.65 (m, 4H), 4.70 (m, 4H), 7.4–7.7 (m, 20H,
Ph). 31P-{1H}-NMR, l: 44.1 (s). Complex 2: yield 60%.
1
2.45; S, 5.5%. H-NMR, l: 4.6 (m, 8H), 7.3–7.7 (m,
20H, Ph). 31P-{1H}-NMR, l: 45.7 (s).
3.1.5. [(v-dptpf){Au(C6F5)3}2] (6) or
[(v-dptpf){Au(C6F5)2Cl}2] (7)
To a solution of [Au(C6F5)3(OEt2)] (0.154 g, 0.2
mmol) or [Au(C6F5)2Cl]2 (0.113 g, 0.1 mmol) in
dichloromethane (20 cm3) was added dptpf (0.062 g, 0.1
mmol) and the mixture was stirred for 1 h. Concentra-
\
M
14 ohm−1 cm2 mol−1. Elemental analysis (%),
Found: C, 40.95; H, 2.1; S, 4.75. Calc. for

14
M.C. Gimeno et al. / Journal of Organometallic Chemistry 596 (2000) 10–15
Table 3
p-F, J(FF) 20 Hz), −161.0 (m, 2F, m-F); −122.9 (m,
2F, o-F), −157.2 (t, 1F, p-F, J(FF) 20.1 Hz), −161.6
(m, 2F, m-F).
Details of data collection and structure refinement for complexes 5
and 7
Compound
5
7.3CH2Cl2
Chemical formula C34H26Au2Cl4FeP2S2 C61H34Au2Cl8F20FeP2S2
3.2. Crystallography
Crystal habit
Crystal size (mm) 0.4×0.3×0.2
Crystal system
Space group
Orange prism
Yellow prism
0.4×0.4×0.3
Monoclinic
C2/c
29.705(3)
14.955(2)
17.658(2)
90
115.113(12)
90
7103.1(14)
4
The crystals were mounted in inert oil on a glass fibre
and transferred to the cold gas stream of a Siemens P4
diffractometer equipped with an LT-2 low-temperature
attachment. Data were collected using monochromated
Trigonal
P3221
12.715(2)
12.715(2)
38.197(6)
90
,
a (A)
,
b (A)
,
c (A)
,
Mo–Ka radiation (u=0.71073 A). Scan type ꢀ. Cell
a (°)
i (°)
k (°)
constants were refined from setting angles of ca. 60
reflections in the range 2q 10–25°. Psi-scans were ap-
plied for both complexes. The structures were solved by
the heavy-atom method and refined on F2 using the
programs SHELXL-93 (5) or -97 (7) [21]. For 7, all
non-hydrogen atoms were refined anisotropically; for 5,
idealised isotropic rings were employed. Hydrogen
atoms were included using a riding model.
90
120
3
,
U (A )
Z
5348(2)
6
2.147
1152.19
3264
Dcalc. (Mg m−3
M
F(000)
)
1.903
2034.65
3904
T (°C)
−100
50
2.147
−100
50
4.843
2qmax (°)
v (Mo–Ka)
(mm−1
)
3.2.1. Special refinement details
Transmission
No. of reflections 6120
measured
0.843–0.972
0.815–0.971
6499
For 5, the absolute structure (and thus the sense of
the three-fold screw axis) was determined by an x
refinement; x=0.00(2). For both structures, a system
of restraints to light-atom displacement-factor compo-
nents and (for 7 additionally) to local ring symmetry
was used. The solvent areas were ill defined; one
molecule is disordered over an inversion centre. Further
details of the data collection are given in Table 3.
No. of unique
reflections
5614
6202
Rint
0.058
0.037
0.044
0.105
a
R
(F, F\4|(F)) 0.058
wR b(F2, all
0.112
reflections)
No. of parameters 173
447
No. of restraints
34
0.842
1.424
367
0.908
1.97
c
S
−3
,
Max. Dz (e A
)
4. Supplementary material
a R(F)=ꢀꢁFoꢂ−ꢂFcꢁ/ꢀꢂFoꢂ.
b wR(F2)=[ꢀ{w(Fo2−Fc2)2}/ꢀ{w(Fo2)2}]0.5
; w
−1=|2(Fo2)+(aP)2
Complete crystallographic data (excluding structure
factors) have been deposited at the Cambridge Crystal-
lographic Data Centre under the numbers CCDC
125989 (5) and CCDC 125988 (7). Copies can be ob-
tained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (Fax: +44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk).
+bP, where P=[Fo2+2Fc2]/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.
tion of the solution to ca. 5 cm3 and addition of diethyl
ether (10 cm3) gave complexes 6 and 7 as orange or
yellow solids, respectively. Complex 6: yield 86%. \M
14 ohm−1 cm2 mol−1. Elemental analysis (%), Found:
Acknowledgements
C,
41.25;
H,
0.95;
S,
2.95.
Calc.
for
1
C70H28Au2F30FeP2S2: C, 41.75; H, 1.4; S, 3.15%. H-
NMR, l: 4.36 (m, 4H), 4.57 (m, 4H), 7.4–7.7 (m, 20H,
Ph). 31P-{1H}-NMR, l: 40.4 (s). 19F-NMR, l: −120.4
(m, 4F, o-F), −157.5 (t, 2F, p-F, J(FF) 20.6 Hz),
−161.5 (m, 4F, m-F); −122.3 (m, 2F, o-F), −157.3
(t, 1F, p-F, J(FF) 20.6 Hz), −161.7 (m, 2F, m-F).
We thank the Direccio´n General de Ensen˜anza Supe-
rior (No. PB97-1010-C02-01) and the Fonds der
Chemischen Industrie for financial support.
References
Complex 7: yield 78%. \M 71 ohm−1 cm2 mol−1
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