Synthesis of [Au2(SC6F5)2(μ-dppf)] and [Au2(μ-SC6F5)(μ-dppf)] (dppf = 1,1′-bis(diphenylphosphino)ferrocene). Reactivity toward various metallic fragments

Article abstract of DOI:10.1021/om9901372

The reaction of [Au₂Cl₂(μ-dppf)] (dppf = 1,1′-bis(diphenylphosphino)ferrocene) with 2 equiv of pentafluorobenzenethiol in the presence of K₂CO₃ leads to the gold(I) thiolate derivative [Au₂(SC₆F₅)₂(μ-dppf)] (1). Complex 1 reacts with [Au(OClO₃)(PR₃)] in a 1:2 or 1:4 molar ratio to give [Au₄(μ₃-SC₆F₅) ₂(μ-dppf)(PR₃)₂](ClO₄) ₂ (PR₃ = PPh₃ (2), PPh₂Me (3)) or [Au₆(μ₄-SC₆F₅) ₂-(μ-dppf)(PR₃)₄](ClO₄) ₄ (PR₃ = PPh₃ (4), PPh₂Me (5)), in which the thiolate ligands bridge two or three gold atoms, respectively. The treatment of 1 with [Au(C₆F₅)₃OEt₂] affords the mixed gold(I)-gold(III) species [Au₄-(μ₃-SC₆F₅) ₂(C₆F₅)₆(μ-dppf)] (6). Heterometallic derivatives have been obtained by reaction of 1 with copper or mercury salts and are of the type [Au₂-Cu(μ₃-SC₆F₅) ₂Cl(μ-dppf)(PPh₃)] (7), [Au₆Cu₂(μ₃-SC₆F₅) ₆(μ-dppf)₃](PF₆)₂ (8), or [Au₂Hg(μ₃-SC₆F₅) ₂X₂(μ-dppf)] (X = Cl (9), 1 (10)). The reaction of 1 with 1 equiv of AgClO₄ gives a precipitate of [Ag(SC₆F₅)]_n and the complex [Au₂(μ-SC₆F₅)(μ-dppf)]ClO₄ (11) with the thiolate ligand bridging both gold atoms. By reaction of 11 with the gold(III) derivative [Au(C₆F₅)₂-(OEt₂) ₂]ClO₄ the complex [Au₅(C₆F₅)₂(μ₃-SC ₆F₅)₂(μ-dppf)₂](ClO ₄)₃ 12 can be isolated. The complexes 6 and 11 have been characterized by X-ray diffraction studies.

Full text of DOI:10.1021/om9901372

3142
Organometallics 1999, 18, 3142-3148
Syn th esis of [Au 2(SC6F 5)2(µ-d p p f)] a n d
[Au 2(µ-SC6F 5)(µ-d p p f)] (d p p f )
1,1′-Bis(d ip h en ylp h osp h in o)fer r ocen e). Rea ctivity tow a r d
Va r iou s Meta llic F r a gm en ts
Olga Crespo,† Fernando Canales,† M. Concepcio´n Gimeno,† Peter G. J ones,‡ and
Antonio Laguna*,†
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain, and Institut fu¨r Anorganische
und Analytische Chemie der Technischen Universita¨t, Postfach 3329,
D-38023 Braunschweig, Germany
Received February 26, 1999
The reaction of [Au2Cl2(µ-dppf)] (dppf ) 1,1′-bis(diphenylphosphino)ferrocene) with 2 equiv
of pentafluorobenzenethiol in the presence of K2CO3 leads to the gold(I) thiolate derivative
[Au2(SC6F5)2(µ-dppf)] (1). Complex 1 reacts with [Au(OClO3)(PR3)] in a 1:2 or 1:4 molar ratio
to give [Au4(µ3-SC6F5)2(µ-dppf)(PR3)2](ClO4)2 (PR3 ) PPh3 (2), PPh2Me (3)) or [Au6(µ4-SC6F5)2-
(µ-dppf)(PR3)4](ClO4)4 (PR3 ) PPh3 (4), PPh2Me (5)), in which the thiolate ligands bridge
two or three gold atoms, respectively. The treatment of 1 with [Au(C6F5)3OEt2] affords the
mixed gold(I)-gold(III) species [Au4(µ3-SC6F5)2(C6F5)6(µ-dppf)] (6). Heterometallic derivatives
have been obtained by reaction of 1 with copper or mercury salts and are of the type [Au2-
Cu(µ3-SC6F5)2Cl(µ-dppf)(PPh3)] (7), [Au6Cu2(µ3-SC6F5)6(µ-dppf)3](PF6)2 (8), or [Au2Hg(µ3-
SC6F5)2X2(µ-dppf)] (X ) Cl (9), I (10)). The reaction of 1 with 1 equiv of AgClO4 gives a
precipitate of [Ag(SC6F5)]n and the complex [Au2(µ-SC6F5)(µ-dppf)]ClO4 (11) with the thiolate
ligand bridging both gold atoms. By reaction of 11 with the gold(III) derivative [Au(C6F5)2-
(OEt2)2]ClO4 the complex [Au5(C6F5)2(µ3-SC6F5)2(µ-dppf)2](ClO4)3 12 can be isolated. The
complexes 6 and 11 have been characterized by X-ray diffraction studies.
In tr od u ction
interest in these compounds and in particular of gold
thiolate complexes.5
Thiolate compounds are the subject of increasing
interest because of their versatile chemistry; worthwhile
topics for study include the potential of thiolate com-
plexes with respect to S-C bond cleavage reactions and
desulfurization,1 the novel structures of some coordina-
tion complexes,2 and the possibility of stabilization of
unusual oxidation states. Applications in the study of
biological systems3 and use in medicine as antiarthritric
or cancerostatic drugs4 also contribute to the growing
Although numerous transition-metal complexes con-
taining the pentafluorobenzenethiolate ligand have been
reported,6 not many gold derivatives have been de-
scribed thus far. Anionic derivatives of the type
[Au(SC6F5)2]-, [AuCl(SC6F5)]-, [Au(SC6F5)4]-, and
[Au2(SC6F5)6]2- were described 20 years ago.7 Since then
only the heterobimetallic derivatives [(C5Me5)M(µ-
SC6F5)2AuCl2]Cl (M ) Rh, Ir)8 or the salts [AuLn][CpM-
(SC6F5)4] (M ) Mo, W; L ) PR3, diphosphine),9 where
no coordination of the gold center to the thiolate ligand
could take place, have been described.
† Universidad de Zaragoza-CSIC.
‡ Institut fu¨r Anorganische und Analytische Chemie der Technis-
chen Universita¨t Braunschweig.
Here we report on the synthesis of several homo- and
heterometallic complexes with the pentafluorobenzene-
thiolate ligand. Several coordination modes and various
structural frameworks are achieved; different metals or
(1) (a) Massoth, F. E. Adv. Catal. 1987, 27, 265. (b) Nishioka, M.
Energy Fuels 1988, 2, 214.
(2) (a) Dance, I. G. Polyhedron 1986, 5, 1037. (b) Blower, P. J .;
Dilworth, J . R. Coord. Chem. Rev. 1987, 76, 121. (c) Stephan, D. W.;
Nadasdi, T. T. Coord. Chem. Rev. 1996, 147, 147.
(3) (a) Steifel, E. I. Prog. Inorg. Chem. 1977, 22, 1. (b) Robson, R.
L.; Eady, R. R.; Richardson, T. H.; Miller, R. W.; Hawkins, M.; Postage,
J . R. Nature 1986, 322, 388. (c) Kustin, K.; Macara, I. G. Comments
Inorg. Chem. 1982, 2, 1. (d) Hales, B. J .; Case, E. E.; Morningstar, J .
E.; Dzeda, M. F.; Manterer, L. A. Biochemistry 1986, 25, 7251.
(4) (a) Smith, W. E.; Reglinski, J . Perspec. Bioinorg. Chem. 1991, 1,
183. (b) Parish, R. V.; Cottrill, S. M. Gold Bull. 1987, 20, 3. (c) Haynes,
D. R.; Whitehouse, M. W. In New Developments in Antirheumatic
Therapy; Rainsford, K. D., Velo, G. P., Eds.; Kluwer: Dordrecht, The
Netherlands, 1989; Chapter 8, p 207. (d) Sutton, B. M.; McGusty, E.;
Walz, D. T.; DiMartino, M. J . J . Med. Chem. 1972, 15, 1095. (e) Sutton,
B. M. Gold Bull. 1986, 19, 15. (f) Simon, T. D.; Kunishima, D. H.;
Vibert, D. H.; Lorber, A. Cancer Res. 1981, 41, 94. (g) Mirabeli, C. K.;
J ohnson, R. K.; Sung, C. M.; Faucette, L.; Muirhead, K.; Crooke, S. T.
Cancer Res. 1985, 45, 32. (h) Ojada, K.; Patterson, B. K.; Ye, S.-Q.;
Gurney, M. E. Virology 1993, 192, 631.
(5) Gold. Progress in Chemistry, Biochemistry and Technology;
Schmidbaur, H., Ed.; Wiley: New York, 1999.
(6) See for example: (a) Uso´n, R.; Fornie´s, J .; Sanz, J . F.; Uso´n, M.
A.; Uso´n, I.; Herrero, S. Inorg. Chem. 1997, 36, 1912. (b) Uso´n, R.;
Fornie´s, J .; Uso´n, M. A.; Toma´s, M.; Iban˜ez, M. A. J . Chem. Soc., Dalton
Trans. 1994, 401. (c) Garcia, J . J .; Torrens, H.; Adams, H.; Bailey, N.
A.; Shacklady, A.; Maitlis, P. M. J . Chem. Soc., Dalton Trans. 1993,
1529. (d) Fonseca, I.; Herna´ndez, E.; Sanz-Aparicio, J .; Terreros, P.;
Torrens, H. J . Chem. Soc., Dalton Trans. 1994, 781.
(7) Muller, M.; Clark, R. J . H.; Nyholm, R. S. Transition Met. Chem.
1978, 3, 369.
(8) Garcia, J . J .; Herna´ndez, M. L.; Torrens, H.; Gutierrez, A.; del
R´ıo, F. Inorg. Chim. Acta 1995, 230, 173.
(9) Davidson, J . L.; Lindsell, W. E.; McCullough, K. J .; McIntosh, C.
H. Organometallics 1995, 14, 3497.
10.1021/om9901372 CCC: $18.00 © 1999 American Chemical Society
Publication on Web 07/17/1999

Synthesis and Reactivity of Gold Thiolates
Organometallics, Vol. 18, No. 16, 1999 3143
Sch em e 1a
a
Legend: (i) 2 HSC6F5 + K2CO3: (ii) 2 [Au(OClO3)PR3]: (iii) 2 [Au(C6F5)3(OEt2)]; (iv) 4 [Au(OClO3)PR3].
the same metal in different oxidation states are coor-
dinated to the same thiolate ligand. The crystal struc-
tures of the complexes [Au4(µ3-SC6F5)2(C6F5)6(µ-dppf)]
and [Au2(µ-SC6F5)(µ-dppf)]ClO4 are reported.
tion with [Au(OClO3)(PR3)] in a 1:2 or 1:4 molar ratio
affords polynuclear derivatives with a µ3-SC6F5 ligand,
[Au4(µ3-SC6F5)2(µ-dppf)(PR3)2](ClO4)2 (PR3 ) PPh3 (2),
PPh2Me (3)), or with a µ4-SC6F5 ligand, [Au6(µ4-SC6F5)2-
(µ-dppf)(PR3)4](ClO4)4 (PR3 ) PPh3 (4), PPh2Me (5)).
Resu lts a n d Discu ssion
Complexes 2-5 are air- and moisture-stable orange
solids that behave as 1:2 or 1:3 electrolytes, respectively.
In their IR spectra the bands for the pentafluorophenyl
group and the ν(C-S) vibration appear in positions close
to those cited for complex 1. Other bands correspond to
the anionic perchlorate at 1100 (br, vs) and 620 (m) cm-1
and to ν(Au-S) at 334 (w) (2), 330 (w) (3), 334 (w) (4),
and 324 (w) cm-1 (5).
In the 31P{1H} NMR of complexes 2 and 3 in CDCl3
at room temperature two signals appear that can be
assigned to the two different phosphorus environments
(PR3 and dppf). When the experiment is carried out at
-55 °C, four signals can be observed, two of them with
lower intensity. If we take into account the unshared
lone pair of electrons at the sulfur atom, this center
must have a chiral tetrahedral conformation, since the
four substituents are different. Consequently, in solu-
tion different conformational isomers must exist; de-
pending on the conformation of each sulfur center three
diastereoisomers must be present: R,R, S,S, and R,S.
The first two must have the same NMR signals, and
the other must be different. Then the four signals
observed in the 31P NMR spectra can be explained by
the presence of two diastereoisomers and the different
intensity of the signals is due to the different abundance
of the two diastereoisomers. At room temperature we
The reaction of [Au2Cl2(µ-dppf)] (dppf ) 1,1′-bis-
(diphenylphosphino)ferrocene) with 2 equiv of pen-
tafluorobenzenethiol, HSC6F5, in dichloromethane with
an excess of K2CO3 leads to the dinuclear thiolate gold-
(I) derivative [Au2(SC6F5)2(µ-dppf)] (1) (see Scheme 1).
Complex 1 is an air- and moisture-stable orange solid
that behaves as a nonconductor in acetone solution. The
IR spectrum shows the ν(Au-S) vibrations at 335 (w)
and 312 (w) cm-1 and those arising at the pentafluo-
rophenyl group of the thiolate ligand at 1510 (vs), 1505
(vs), and 970 (vs) cm-1; ν(C-S) appears at 854 (s) cm-1
.
The 1H NMR spectrum displays two multiplets for the
R- and â-protons of the cyclopentadienyl rings and a
broad multiplet for the phenyl protons. The 31P{1H}
NMR shows one singlet for the two equivalent phos-
phorus atoms, and the 19F NMR spectrum presents
-
three resonances for the SC6F5 group, two multiplets
for the ortho and meta fluorines and a triplet for the
para fluorine. The positive-ion liquid secondary mass
spectrum (LSIMS+) of 1 shows the molecular peak at
m/z 1346, although with very low intensity (1%); a more
intense peak (30%) at m/z 1147 corresponds to the loss
of one thiolate group.
Complex 1 is a suitable starting material since it can
react with various metallic fragments. Thus, the reac-

3144 Organometallics, Vol. 18, No. 16, 1999
Crespo et al.
only observed one isomer, which may reasonably be
attributed to fast equilibria for pyramidal inversion, as
previously studied e.g. for amines, phosphines, arsines,
sulfoxides, or sulfonium salts bearing three different
substituents.10 The 1H NMR spectra of 2 and 3 show
two broad signals at room temperature that split into
four at -55 °C; these signals are still broad and may
be the reason both diastereoisomers are not observed.
The resonances have the same intensity ratio and are
assigned to the different R- and â-protons of the cyclo-
pentadienyl ring, which are only equivalent by fluxion-
ality. The 19F spectra at room temperature present the
typical pattern of a pentafluorophenyl ring with two
multiplets for the ortho and meta fluorines and a triplet
for the para fluorine. At low temperature the signals
are very broad, and then the two diastereoisomers
cannot be distinguished.
F igu r e 1. Structure of the molecule of complex 6 in the
crystal, showing the atom-numbering scheme of the asym-
metric unit. H atoms are omitted for clarity.
The room-temperature 31P{1H} NMR spectra of com-
plexes 4 and 5 show two resonances arising from the
two different types of phosphorus atoms. At -55 °C each
resonance splits into two as a consequence of the
inequivalence of the two “Au2(µ-SC6F5)(PR3)2” units; this
is corroborated in the low-temperature 19F NMR spec-
tra, because both thiolate groups are then inequivalent.
The 1H NMR spectra at room temperature show two
broad resonances for the R- and â-protons of the cyclo-
pentadienyl ring; at -55 °C seven signals appear
because of the inequivalence of all Cp protons, the
resonances for two protons being overlapped. The in-
equivalence of the thiolate groups and in the phosphorus
atoms, we believe, is a consequence of the different
gold-gold interactions that can be observed in the low-
temperature NMR spectra. We have previously observed
this inequivalence in this type of complex.11
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 6
Au(1)-P
2.267(2)
2.048(7)
2.056(7)
1.752(7)
Au(1)-S
Au(2)-C(41)
Au(2)-S
2.339(2)
2.049(7)
2.380(2)
Au(2)-C(51)
Au(2)-C(61)
S-C(31)
P-Au(1)-S
176.62(7) C(51)-Au(2)-C(41)
87.9(3)
C(51)-Au(2)-C(61)
C(51)-Au(2)-S
C(61)-Au(2)-S
C(11)-P-Au(1)
C(31)-S-Au(1)
Au(1)-S-Au(2)
89.6(3)
176.3(2)
86.8(2)
C(41)-Au(2)-C(61) 177.5(3)
C(41)-Au(2)-S
C(1)-P-Au(1)
95.7(2)
114.6(2)
111.9(3)
107.1(2)
112.2.(3) C(21)-P-Au(1)
109.8.(2) C(31)-S-Au(2)
99.77(7) C(42)-C(41)-Au(2) 124.9(6)
C(46)-C(41)-Au(2) 120.9(6)
C(56)-C(51)-Au(2) 120.3(6)
C(66)-C(61)-Au(2) 120.7(6)
C(52)-C(51)-Au(2) 122.3(6)
C(62)-C(61)-Au(2) 124.0(5)
significant interaction. The gold atoms bonded to the
same thiolate group are gold(I) and gold(III), but
nevertheless this Au‚‚‚Au distance is quite short, 3.608-
(2) Å, and the angle Au(I)-S-Au(III) is 99.77(7)°,
narrower than the others around the sulfur atom (Au-
S-C ) 109.8(2), 107.1(2)°). This may indicate the
presence of a weak interaction between the gold(I) and
the gold(III) centers. We have previously pointed out
this possibility, as indicated by short gold(I)-gold(III)
distances in some of our complexes and corroborated by
theoretical studies.12,13 The geometry of the gold(I) and
gold(III) centers is, as expected, linear and square
planar, respectively, with only slight distortions. The
Au(I)-S distance is 2.339(2) Å and compares well with
values found in other gold(I) thiolate complexes such
as [Au2(µ-SCH2Ph)(PPh3)2] (2.331-2.345 Å).14 The Au-
(III)-S bond length is 2.380(2) Å, but there are not
many examples of gold(III) thiolate derivatives for
comparison; in the complex [Au2Cl4(µ-SPh)2]14 the dis-
tances are shorter, 2.332(5) and 2.339(5) Å, but the
difference may arise from the trans influence of the
phosphine being higher than that of the chloro ligand.
The reaction of complex 1 with other metal complexes
affords heterometallic derivatives. Thus, the treatment
of 1 with [CuCl(PPh3)]4 gives the four-coordinate copper
compound [Au2Cu(µ3-SC6F5)2Cl(µ-dppf)(PPh3)] (7) (see
Scheme 2). Complex 7 is slightly conducting in acetone
The reaction of 1 with 2 equiv of [Au(C6F5)3(OEt2)]
gives a mixed gold(I)-gold(III) derivative with a bridg-
ing thiolate ligand, [Au4(µ3-SC6F5)2(C6F5)6(µ-dppf)] (6).
Complex 6 is an air- and moisture-stable orange solid
that behaves as a nonconductor in acetone solutions. Its
IR spectrum presents absorptions from the pentafluo-
robenzenethiolate unit at 984 (s) and 853 (m) cm-1 and
from the pentafluorophenyl rings bonded to gold(III) at
1510 (vs) and 971 (vs) cm-1
.
The 31P{1H} NMR spectrum shows one singlet for the
equivalent dppf phosphorus atoms. In the 1H NMR
spectrum the R- and â-protons of the cyclopentadienyl
rings appears as multiplets. The 19F NMR spectrum
presents three different pentafluorophenyl groups; one
corresponds to the thiolate ligand and the other two to
the cis and trans groups of the “Au(C6F5)3” unit. In the
LSIMS+ mass spectrum the molecular peak appears at
m/z 2742 (6%).
The structure of 6 has been confirmed by X-ray
diffraction studies; the molecule is shown in Figure 1.
A selection of bond lengths and angles is collected in
Table 1. The iron atom lies on a twofold axis, and thus
only half of the molecule corresponds to the asymmetric
unit. Short gold-gold contacts are usually observed for
gold(I) centers, but the gold(I)-gold(I) distance in 6 is,
at 3.834(2) Å, probably too long to be considered a
(12) Canales, F.; Gimeno, M. C.; Laguna, A.; J ones, P. G. Organo-
metallics 1996, 15, 3412.
(13) Calhorda, M. J .; Canales, F., Gimeno, M. C.; J ime´nez, J .; J ones,
P. G.; Laguna, A.; Veiros, L. F. Organometallics 1997, 16, 3837.
(14) Wang, S.; Fackler, J . P., J r. Inorg. Chem. 1990, 29, 4404.
(10) Advanced Organic Chemistry. Reactions, Mechanism and Struc-
ture, 4th ed.; J . March, J ., Ed.; Wiley-Interscience: New York, 1992.
(11) Canales, F.; Gimeno, M. C.; Laguna, A.; J ones, P. G. J . Am.
Chem. Soc. 1996, 118, 4839.

Synthesis and Reactivity of Gold Thiolates
Organometallics, Vol. 18, No. 16, 1999 3145
Sch em e 2a
I
a
Legend: (i) [CuCl(PPh3)]4; (ii) HgCl2 or HgI2; (iii) AgClO4; (iv) [Cu(NCMe)4]PF6; (v) [Au(C6F5)2(OEt2)2]ClO4.
Sch em e 3
solutions, 22 Ω-1 cm2 mol-1, which could be due to
chloride dissociation.
In the 31P{1H} NMR spectrum at room temperature
two broad signals appear that sharpen into two singlets
at 32.3 and -14.3 ppm at low temperature. The 1H
NMR spectrum shows four broad multiplets for the
cyclopentadienyl protons; at -55 °C the signals split into
poorly resolved multiplets for the eight different Cp
protons. Usually, complexes with disubstituted fer-
rocene ligands show two multiplets in the 1H NMR
spectra for the R- and â-protons of the cyclopentadienyl
rings, even though in the solid state (because of the
different ring conformations) the eight protons are
inequivalent. This inequivalence is sometimes observed,
as in this case, at low temperature. The 19F NMR
spectrum shows only one type of pentafluorophenyl
phosphorus of the dppf in the chelating and bridging
group.
metallacycles, respectively. The 1H NMR spectrum
shows two broad multiplets for the R- and â-protons of
the Cp rings, which split into four multiplets at low
temperature. The 19F NMR spectrum at room temper-
ature is also simple and contains the three typical
resonances of a pentafluorophenyl group and a doublet
for the PF6 anion. At -55 °C the spectrum is compli-
cated, probably because of the presence of several
isomers that are in rapid equilibrium at room temper-
ature (Scheme 3). The three isomers (8a -c) are detected
with different intensities.
The reaction of 1 with [Cu(NCMe)4]PF6 in any molar
ratio gives the polynuclear complex [Au6Cu2(µ3-SC6F5)6-
(µ-dppf)3](PF6)2 (8), which has two copper atoms sur-
rounded by three thiolate ligands. Its IR spectrum
presents the absorption due to the PF6 anion at 853 (s)
cm-1; the bands for the thiolate ligand appear at 1510
(vs), 977 (vs), and ca. 855 cm-1 (overlapped with PF6)
and the ν(Au-S) vibrations at 340 (w) and 314 (w) cm-1
.
The 31P{1H} NMR at room temperature consists of a
singlet, but when the experiment is carried out at -55
°C the signal splits into two singlets with a different
ratio, approximately 2:1, which can be assigned to the
Complex 1 also reacts with HgX2 to give the hetero-
metallic species [Au2Hg(µ3-SC6F5)2X2(µ-dppf)] (X ) Cl

3146 Organometallics, Vol. 18, No. 16, 1999
Crespo et al.
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for Com p lex 11
Au(1)-P(1)
Au(1)-S(1)
Au(1)-Au(2)
Au(2)-P(2)
Au(2)-S(1)
Au(2)-Au(3)
Au(3)-P(3)
Au(3)-S(2)
Au(3)-Au(4)
Au(4)-P(4)
Au(4)-S(2)
S(1)-C(61)
S(2)-C(121)
2.260(6)
2.352(6)
2.9610(16)
2.273(6)
2.374(6)
2.9666(14)
2.280(5)
2.343(5)
2.9788(14)
2.248(6)
2.352(5)
1.74(2)
P(1)-C(21)
P(1)-C(31)
P(1)-C(11)
P(2)-C(36)
P(2)-C(51)
P(2)-C(41)
P(3)-C(81)
P(3)-C(91)
P(3)-C(71)
P(4)-C(96)
P(4)-C(101)
P(4)-C(111)
1.80(2)
1.81(2)
1.823(19)
1.78(2)
1.82(3)
1.84(2)
1.78(2)
1.80(2)
1.83(2)
1.802(19)
1.82(2)
1.85(2)
1.81(2)
P(1)-Au(1)-S(1)
P(1)-Au(1)-Au(2)
S(1)-Au(1)-Au(2)
P(2)-Au(2)-S(1)
P(2)-Au(2)-Au(1)
S(1)-Au(2)-Au(1)
P(2)-Au(2)-Au(3)
S(1)-Au(2)-Au(3)
175.4(2)
Au(3)-S(2)-Au(4)
78.75(16)
105.3(8)
107.3(9)
105.0(8)
111.6(6)
111.2(6)
115.7(6)
103.9(9)
108.2(8)
104.9(9)
111.1(6)
115.5(7)
112.7(6)
106.9(8)
108.4(8)
106.1(8)
114.3(6)
110.2(5)
110.7(6)
105.4(9)
104.6(8)
124.42(16) C(21)-P(1)-C(31)
51.53(15) C(21)-P(1)-C(11)
170.9(2)
120.28(17) C(21)-P(1)-Au(1)
50.88(14) C(31)-P(1)-Au(1)
104.88(17) C(11)-P(1)-Au(11)
83.83(15) C(36)-P(2)-C(51)
C(31)-P(1)-C(11)
F igu r e 2. Perspective view of the two linked cations of
complex 11, with the atom-labeling scheme. H atoms are
omitted for clarity.
Au(1)-Au(2)-Au(3) 134.67(4)
C(36)-P(2)-C(41)
C(51)-P(2)-C(41)
(9), I (10)). These compounds are air- and moisture-
stable orange solids that are nonconductors in acetone
solution, although complex 10 has a conductivity of 32
Ω-1 cm2 mol-1, probably due to dissociation of the
halogen in acetone. In the IR spectra the bands for the
thiolate appear at 1510 (vs), 976 (vs) and 857 (s) cm-1
(9) and at 1511 (vs), 977 (vs), and 852 (s) cm-1 (10).
The 31P{1H} NMR spectra show only one resonance
because of the equivalence of the phosphorus atoms; in
the 1H NMR spectra two multiplets for the R- and
â-protons of the cyclopentadienyl protons appear and
the 19F NMR spectra show that both pentafluorophenyl
groups are also equivalent.
P(3)-Au(3)-S(2)
P(3)-Au(3)-Au(2)
S(2)-Au(3)-Au(2)
P(3)-Au(3)-Au(4)
S(2)-Au(3)-Au(4)
169.8(2)
97.36(15) C(36)-P(2)-Au(2)
85.02(14) C(51)-P(2)-Au(2)
122.52(14) C(41)-P(2)-Au(2)
50.77(13) C(81)-P(3)-C(91)
Au(2)-Au(3)-Au(4) 130.49(4)
C(81)-P(3)-C(71)
P(4)-Au(4)-S(2)
172.02(18) C(91)-P(3)-C(71)
121.70(14) C(81)-P(3)-Au(3)
50.49(13) C(91)-P(3)-Au(3)
109.4(5)
107.9(5)
P(4)-Au(4)-Au(3)
S(2)-Au(4)-Au(3)
C(61)-S(1)-Au(1)
C(71)-P(3)-Au(3)
C(96)-P(4)-C(101)
C(61)-S(1)-Au(2)
Au(1)-S(1)-Au(2)
77.59(17) C(96)-P(4)-C(111)
C(121)-S(2)-Au(3) 110.3(5)
C(121)-S(2)-Au(4) 106.0(5)
C(101)-P(4)-Au(4) 114.5(6)
C(101)-P(4)-C(111) 106.3(9)
C(96)-P(4)-Au(4)
C(111)-P(4)-Au(4)
109.9(5)
115.2(6)
ideal tetrahedral values. These Au(I)-S-Au(I) angles
are much narrower than that of complex 6 (see above),
which corresponds to Au(I)-S-Au(III).
The reaction of 1 with silver salts involves elimination
of one thiolate group as [Ag(SC6F5)]n and formation of
a cyclic complex with a bridging thiolate ligand, [Au2-
(µ-SC6F5)(µ-dppf)]ClO4 (11). Its IR spectrum shows the
presence of the ClO4 anion with bands at 1100 (vs, br)
and 622 (m) cm-1; the thiolate absorptions appear at
1115 (s), 978 (m), and 850 (m) cm-1. The conductivity
of 11 corresponds to a 1:1 electrolyte.
The NMR spectra are similar to those of the other
complexes, showing equivalent phosphorus atoms for
31P, two multiplets for the cyclopentadienyl protons for
1H, and only one type of pentafluorophenyl group for
19F. In the LSIMS+ spectrum the molecular cation peak
at m/z 1147 is the most intense.
The structure of complex 11 has been determined by
X-ray diffraction studies and is shown in Figure 2. A
selection of bond lengths and angles is collected in Table
2. The asymmetric unit consists of two independent
formula units, which show short intra- and intermo-
lecular gold-gold contacts. One discrete cation of com-
plex 11 consist of two gold atoms bridged by the
diphosphine and the thiolate ligands. The intramolecu-
lar Au-Au distances are 2.9610(16) and 2.9788(14) Å,
and the intermolecular Au(2)-Au(3) distance is of the
same order, 2.9666(14) Å. The solid-state structure is
different from that obtained for the complex [Au2(µ-
SCH2Ph)(PPh3)2], in which the thiolate ligand bridges
two AuPPh3 units in a similar manner, but the associa-
tion of two cations through gold-gold interactions leads
to a six-membered ring, with a chair conformation.14 The
Au-S-Au angles in 11 are very narrow, 77.59(17) and
78.75(16)°, whereas the Au-S-C angles are close to
The four gold atoms have a slightly distorted linear
geometry; the largest deviations are 10.2 and 9.1° for
Au(3) and Au(2) respectively, the gold atoms with both
intra- and intermolecular gold-gold interactions. The
Au-S distances range from 2.343(5) to 2.374(6) Å; they
are somewhat dissimilar, although the difference may
not be significant. They are of the same order as those
found in complex 6.
Complex 11 can further react with other metallic
centers; thus, the treatment with [Au(C6F5)2(OEt2)2]-
ClO4 in the molar ratio 2:1 leads to the polynuclear
compound [Au5(C6F5)2(µ3-SC6F5)2(µ-dppf)2](ClO4)3 (12).
Complex 12 is an air- and moisture-stable orange solid
that behaves as a 1:3 electrolyte in acetone solution. The
IR spectrum shows the absorptions arising from pen-
tafluorophenyl groups at 1514 (s), 975 (s), and 851 (s)
cm-1. The vibration ν(Au-S) appears at 314 (w) cm-1
.
The 31P{1H} NMR spectrum of 12 at room tempera-
ture shows one broad resonance that splits into two at
-55 °C; this indicates that both phosphorus atoms of
the diphosphine are inequivalent, conceivably because
of the presence of different gold(I)-gold(I) or gold(I)-
1
gold(III) interactions. In the H NMR spectrum at room
temperature the resonances due to the Cp protons are
very broad, whereas at -55 °C six multiplets appear
because the signals of some of the protons are over-
lapped. The 19F NMR spectrum at room temperature
shows the resonances arising from two types of pen-

Synthesis and Reactivity of Gold Thiolates
Organometallics, Vol. 18, No. 16, 1999 3147
δ -129.9 (m, 4F, o-F), -160.1 (m, 4F, m-F), -154.0 (t, 2F, p-F,
3J (FF) ) 21.33 Hz) ppm. Complex 3: yield 92%. ΛM ) 211
Ω-1 cm2 mol-1. Anal. Found: C, 37.4; H, 2.32; S, 2.60. Calcd
for C72H54Au4Cl2F10O8P4S2: C, 36.96; H, 2.33; S, 2.74. 1H NMR
(room temperature): δ 2.18 (d, 6H, J (PH) ) 10.69 Hz), 4.24
tafluorophenyl groups; however, at low temperature the
signals become broader.
In the LSIMS+ spectrum the molecular peak does not
appear, perhaps because of the high charge of the
complex. The peak arising from the loss of one Au2-
1
(m, 4H, C5H4), 4.64 (m, 4H, C5H4), 7.2-7.6 (m, 40H, Ph). H
2+
(dppf)2 fragment from the molecular cation, [Au3-
NMR (-55 °C): δ 2.14 (d, 6H, J (PH) ) 9.50 Hz), 3.59 (m, 2H,
C5H4), 4.18 (m, 2H, C5H4), 4.75 (m, 2H, C5H4), 5.03 (m, 2H,
C5H4), 7.2-7.6 (m, 40H, Ph) ppm. 31P{1H} NMR (room tem-
perature): δ 19.5 (br, 2P, PPh2Me), 29.4 (s, 2P, dppf). 31P{1H}
NMR (-55 °C) δ 17.0 (s), 19.9 (s), 28.3 (s), 31.2 (s) ppm. 19F
NMR: δ -129.8 (m, 4F, o-F), -160.3 (m, 4F, m-F), -154.3 (t,
(dppf)(C6F5)2(SC6F5)2]+, is observed at m/z 1877 (5%).
Exp er im en ta l Section
In str u m en ta tion . Infrared spectra were recorded in the
range 4000-200 cm-1 on a Perkin-Elmer 883 spectrophotom-
eter using Nujol mulls between polyethylene sheets. Conduc-
tivities 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 microanalyzer. Mass
spectra were recorded on a VG Autospec, with the LSIMS
technique, using nitrobenzyl alcohol as matrix. NMR spectra
were recorded on a Varian Unity 300 spectrometer and a
Bruker ARX 300 spectrometer in CDCl3. Chemical shifts are
cited relative to SiMe4 (1H, external), CFCl3 (19F, external),
and 85% H3PO4 (31P, external).
3
2F, p-F, J (FF) ) 20.73 Hz) ppm.
[Au 6(µ3-SC6F 5)2(µ-d p p f)(P R3)4](ClO4)4 (P R3 ) P P h 3 (4),
P P h 2Me (5)). To a dichloromethane solution (20 mL) of [Au2-
(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) was added [Au(OClO3)-
PPh3] (0.222 g, 0.4 mmol) or [Au(OClO3)PPh2Me] (0.198 g, 0.4
mmol) and the mixture stirred for 15 min. Concentration of
the solution to ca. 5 mL and addition of hexane gave orange
solids of complex 4 or 5. Complex 4: yield 90%. ΛM ) 300.8
Ω-1 cm2 mol-1. Anal. Found: C, 39.95; H, 2.40; S, 1.80. Calcd
for C118H88Au6Cl4F10O16P6S2: C, 39.57; H, 2.48; S, 1.79. 1H
NMR (room temperature): δ 4.27 (m, 4H, C5H4), 4.64 (m, 4H,
C5H4), 7.2-7.7 (m, 80H, Ph). 1H NMR (-55 °C): δ 3.52 (m,
1H, C5H4), 3.64 (m, 1H, C5H4), 4.15 (m, 1H, C5H4), 4.21 (m,
1H, C5H4), 4.74 (m, 1H, C5H4), 4.77 (m, 1H, C5H4), 5.03 (m,
2H, C5H4), 7.2-7.7 (m, 80H, Ph) ppm. 31P{1H} NMR (room
temperature): δ 29.0 (s, 2P, dppf), 33.1 (br, 4P, PPh3). 31P-
{1H} NMR (-55 °C): δ 28.0 (s, 1P, dppf), 28.4 (s, 1P, dppf),
31.0 (s, 2P, PPh3), 33.9 (s, 2P, PPh3) ppm. 19F NMR (room
temperature): δ -129.7 (m, 4F, o-F), -160.0 (m, 4F, m-F),
-153.6 (br, 2F, p-F). 19F NMR (-55 °C): δ -129.2 (m, 2F, o-F),
-129.4 (m, 2F, o-F), -158.8 (m, 4F, m-F), -152.2 (t, 1F, p-F,
3J (FF) ) 21.31 Hz), -152.7 (t, 1F, p-F, 3J (FF) ) 22.15 Hz)
ppm. Complex 5: yield 86%. ΛM ) 314 Ω-1 cm2 mol-1. Anal.
Found: C, 34.99; H, 2.50; S, 1.88. Calcd for C98H80Au6-
Cl4F10O16P6S2: C, 35.31; H, 2.42; S, 1.92. 1H NMR (room
temperature): δ 2.19 (d, 12H, J (PH) ) 10.85 Hz), 4.30 (m, 4H,
C5H4), 4.68 (m, 4H, C5H4), 7.2-7.8 (m, 60H, Ph). 1H NMR (-55
°C): δ 2.08 (br, 6H, PMe), 2.17 (br, 6H, PMe), 3.54 (m, 1H,
C5H4), 3.61 (m, 1H, C5H4), 4.15 (m, 1H, C5H4), 4.20 (m, 1H,
C5H4), 4.75 (m, 1H, C5H4), 5.03 (m, 1H, C5H4), 5.08 (m, 2H,
C5H4), 7.2-7.8 (m, 60H, Ph) ppm. 31P{1H} NMR (room tem-
perature): δ 18.0 (br, 4P, PPh2Me), 28.8 (s, 2P, dppf). 31P{1H}
NMR (-55 °C): 16.4 (s, 2P, PPh2Me), 19.4 (s, 2P, PPh2Me),
28.1 (s, 1P, dppf), 28.2 (s, 1P, dppf) ppm. 19F NMR (room
temperature): δ -129.6 (m, 4F, o-F), -160.5 (m, 4F, m-F),
-153.9 (br, 2F, p-F). 19F NMR (-55 °C): δ -129.3 (m, 2F, o-F),
-129.5 (m, 2F, o-F), -159.0 (m, 2F, m-F), -159.5 (m, 2F, m-F),
-152.7 (t, 1F, p-F, 3J (FF) ) 21.31 Hz), -153.2 (t, 1F, p-F,
3J (FF) ) 22.01 Hz) ppm.
Ma ter ia ls. The starting materials [Au2Cl2(µ-dppf)],15 [Au-
(C6F5)3OEt2],16 [Cu(NCMe)4]PF6,17 and [Au(C6F5)2(OEt2)2]ClO4
18
were prepared by published procedures. [Au(OClO3)PPh3] was
prepared from [AuCl(PPh3)]19 and AgClO4 in dichloromethane
in the molar ratio 1:1; the mixture was stirred for 1 h, and
then the AgCl was filtered off and the solution containing [Au-
(OClO3)PPh3] was used inmediately. Similarly [Au2(OClO3)2-
(µ-dppf)] was obtained from [Au2Cl2(µ-dppf)] and 2 equiv of
AgClO4 in dichloromethane and also used inmediately. All
other reagents were commercially available.
Sa fety Note. Caution! Perchlorate salts of metal complexes
with organic ligands are potentially explosive. Only small
amounts of material should be prepared, and these should be
handled with great caution.
Syn th eses. [Au 2(SC6F 5)2(µ-d p p f)] (1). To a solution of
[Au2Cl2(µ-dppf)] (0.102 g, 0.1 mmol) in dichloromethane (20
mL) was added HSC6F5 (0.029 mL, 0.2 mmol) and K2CO3 (0.69
g, 5 mmol). The mixture was stirred for 2 h and then filtered
to eliminate the salts. The resulting solution was concentrated
to ca. 5 mL, and addition of hexane gave an orange solid of 1.
Yield: 98%. ΛM ) 0.86 Ω-1 cm2 mol-1. Anal. Found: C, 40.57;
H, 1.80; S, 4.96. Calcd for C46H28Au2F10P2S2: C, 41.03; H, 2.10;
S, 4.76. 1H NMR: δ 4.23 (m, 4H, C5H4), 4.67 (m, 4H, C5H4),
7.2-7.6 (m, 20H, Ph) ppm. 31P{1H} NMR: δ 29.1 (s, 2P, dppf)
ppm. 19F NMR: δ -132.8 (m, 4F, o-F), -164.4 (m, 4F, m-F),
3
-162.7 (t, 2F, p-F, J (FF) ) 21.36 Hz) ppm.
[Au 4(µ3-SC6F 5)2(µ-d p p f)(P R3)2](ClO4)2 (P R3 ) P P h 3 (2),
P P h 2Me (3)). To a dichloromethane solution (20 mL) of [Au2-
(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) was added [Au(OClO3)-
PPh3] (0.111 g, 0.2 mmol) or [Au(OClO3)PPh2Me] (0.099 g, 0.2
mmol) and the mixture stirred for 15 min. Concentration of
the solution to ca. 5 mL and addition of hexane gave orange
solids of complex 2 or 3. Complex 2: yield 81%. ΛM ) 197 Ω-1
cm2 mol-1. Anal. Found: C, 40.0; H, 2.11; S, 2.55. Calcd for
[Au 4(µ3-SC6F 5)2(C6F 5)6(µ-d p p f)] (6). To a solution of [Au2-
(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) in dichloromethane (20
mL) was added [Au(C6F5)3OEt2] (0.144 g, 0.2 mmol) and the
mixture stirred for 15 min. Evaporation of the solvent to ca. 5
mL and addition of hexane afforded complex 6 as an orange
solid. Yield: 80%. ΛM ) 10.4 Ω-1 cm2 mol-1. Anal. Found: C,
35.47; H, 0.96; S, 2.34. Calcd for C82H28Au4F40FeP2S2: C, 35.91;
C
82H58Au4Cl2F10O8P4S2: C, 39.97; H, 2.37; S, 2.60. 1H NMR
(room temperature): δ 4.28 (m, 4H, C5H4), 4.66 (m, 4H, C5H4),
7.2-7.6 (m, 50H, Ph). 1H NMR (-55 °C): δ 3.60 (m, 2H, C5H4),
4.17 (m, 2H, C5H4), 4.78 (m, 2H, C5H4), 5.04 (m, 2H, C5H4),
7.2-7.6 (m, 50H, Ph) ppm. 31P{1H} NMR (room tempera-
ture): δ 29.2 (s, 2P, dppf), 33.5 (br, 2P, PPh3). 31P{1H} NMR
(-55 °C): δ 23.3 (s), 28.2 (s), 33.0 (s), 34.7 (s) ppm. 19F NMR:
1
H, 1.02; S, 2.34. H NMR: δ 4.28 (m, 4H, C5H4), 4.74 (m, 4H,
C5H4), 7.4-7.6 (m, 20H, Ph) ppm. 31P{1H} NMR: δ 31.0 (s,
2P, dppf) ppm. 19F NMR: δ -120.0 (m, 8F, o-F), -122.2 (m,
4F, o-F), -129.1 (m, 4F, o-F), -160.6 (m, 4F, m-F), -160.7 (m,
8F, m-F), -161.4 (m, 4F, m-F), -151.3 (t, 2F, p-F, 3J (FF) )
3
21.36 Hz), -156.3 (t, 4F, p-F, J (FF) ) 19.98 Hz), -156.8 (t,
3
2F, p-F, J (FF) ) 19.98 Hz) ppm.
(15) Gimeno, M. C.; Laguna, A.; Sarroca, C.; J ones, P. G. Inorg.
Chem. 1993, 32, 5926.
(16) Uso´n, R.; Laguna, A.; Laguna, M.; J ime´nez, J .; Durana, E.
Inorg. Chim. Acta 1990, 168, 89.
(17) Kubas, G. J . Inorg. Synth. 1990, 28, 68.
(18) Uso´n, R.; Laguna, A.; Arrese, M. L. Synth. React. Inorg. Met.-
Org. Chem. 1984, 14, 369.
[Au 2Cu (µ3-SC6F 5)2Cl(µ-d p p f)(P P h 3)] (7). To a solution of
[Au2(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) in dichloromethane
(20 mL) was added [CuCl(PPh3)]4 (0.036 g, 0.25 mmol), and
the mixture was stirred for 1 h. Evaporation of the solvent to
ca. 5 mL and addition of hexane gave complex 7 as an orange
solid. Yield: 40%. ΛM ) 22 Ω-1 cm2 mol-1. Anal. Found: C,
(19) Uso´n, R.; Laguna, A. Inorg. Synth. 1982, 21, 71.

3148 Organometallics, Vol. 18, No. 16, 1999
Crespo et al.
Ta ble 3. Deta ils of Da ta Collection a n d Str u ctu r e
Refin em en t for Com p lexes 6 a n d 11
45.47; H, 2.55; S, 3.01. Calcd for C64H43Au2CuF10FeClP3S2: C,
45.01; H, 2.54; S, 3.75. H NMR: δ 3,8 (m, br, 2H, C5H4), 4.2
1
(m, br, 2H, C5H4), 4.3 (m, br, 2H, C5H4), 4,5 (m, br, 2H, C5H4),
7.2-7.6 (m, 35H, Ph) ppm. 31P{1H} NMR: δ 32.0 (br, 2P, dppf),
-12.1 (br, 1P, PPh3) ppm. 19F NMR: δ -132.4 (m, br, 4F, o-F),
-163.2 (m, br, 4F, m-F), -161.0 (m, br, 2F, p-F).
6
11‚2.5CH2Cl2
chem formula
C82H28Au4F40FeP2S2 C42.5H32Au2Cl6F5Fe-
O4P2S
orange prism
0.40 × 0.30 × 0.25
monoclinic
C2/c
13.5150(10)
21.974(2)
27.244(3)
94.716(9)
8063.5(13)
4
cryst habit
cryst size/mm
cryst syst
space group
a/Å
orange plate
0.50 × 0.20 × 0.05
monoclinic
P21/c
14.953(5)
30.587(8)
21.606(5)
107.01(2)
9450(5)
8
[Au 6Cu 2(µ3-SC6F 5)6(µ-d p p f)3](P F 6)2 (8). To a solution of
[Au2(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) in dichloromethane
(20 mL) was added [Cu(NCMe)4]PF6 (0.037 g, 0.05 mmol), and
the mixture was stirred for 1 h. Evaporation of the solvent to
ca. 5 mL and addition of hexane gave complex 8 as an orange
solid. Yield: 56%. ΛM ) 200 Ω-1 cm2 mol-1. Anal. Found: C,
37.69; H, 1.43; S, 5.02. Calcd for C114H84Au6Cu2F32Fe3P8S4: C,
b/Å
c/Å
â/deg
U/Å3
1
Z
37.19; H, 1.90; S, 4.31. H NMR (room temperature): δ 4.38
D
calcd/Mg m-3
2.259
2742.82
5136
2.050
1458.16
5568
(m, 12H, C5H4), 4.45 (m, 12H, C5H4), 7.2-7.8 (m, 60H, Ph).
1H NMR (-55 °C): δ 4.0 (m, br, 4H, C5H4), 4.3 (m, br, 12H,
C5H4), 4.5 (m, br, 4H, C5H4), 4.9 (m, 4H, C5H4), 7.2-7.8 (m,
60H, Ph) ppm. 31P{1H} NMR (room temperature): δ 27.8 (br,
6P, dppf); -55 °C, 30.7 (s, 2P, dppf), 29.1 (s, 4P, dppf). 19F NMR
(room temperature): δ -74.0 (d, 12F, PF6, J (PF) ) 713.69 Hz),
-131.6 (br, 12F, o-F), -162.4 (br, 12F, m-F), -158.3 (br, 6F,
p-F). 19F NMR (-55 °C): isomer A, δ -132.1 (m, 8F, o-F, SR1),
-162.9 (m, 8F, m-F, SR1), -158.0 (br, 4F, p-F, SR1), -132.1
(m, 8F, o-F, SR2), -163.0 (m, 8F, m-F, SR2), -158.1 (br, 4F,
p-F, SR2) ppm; isomer B, δ -132.3 (m, 8F, o-F, SR1), -161.4
(m, 8F, m-F, SR1), -156.2 (br, 4F, p-F, SR1), -132.8 (m, 8F,
o-F, SR2), -163.3 (m, 8F, m-F, SR2), -156.8 (br, 4F, p-F, SR2)
ppm.
Mr
F(000)
T/°C
-100
-100
2θmax/deg
µ(Μo KR)/mm-1
transmissn
50
45
7.649
7.010
0.520-0.687
0.265-0.797
15 834
12 113
0.067
no. of rflns measd 10 642
no. of unique rflns 7073
Rint
0.051
0.033
0.063
7068
591
475
0.872
0.904
R(F)a (F > 4σ(F))
Rw(F2)b (all rflns)
no. of rflns used
no. of params
no. of restraints
Sc
0.070
0.171
12113
665
237
0.911
2.469
max ∆F/e Å-3
[Au 2Hg(µ3-SC6F 5)2X2(µ-d p p f)] (X ) Cl (9), I (10)). To a
solution of [Au2(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) in dichlo-
romethane (20 mL) was added HgCl2 (0.027 g, 0.1 mmol) or
HgI2 (0.046 g, 0.1 mmol), and the mixture was stirred for 1 h.
The solution was evaporated to ca. 5 mL, and addition of
hexane gave complex 9 or 10 as orange solids. Complex 9:
a
b
2
R(F)) ∑||Fo| - |Fc||/∑|Fo|. Rw(F2) ) [∑{w(Fo - Fc2)2}/
∑{w(Fo2)2}]0.5; w-1 ) σ2(Fo2) + (aP)2 + bP, where P ) [Fo + 2Fc2]/
2
3 and a and b are constants adjusted by the program. c S )
[∑{w(Fo - Fc2)2}/(n - p)]0.5, where n is the number of data and p
2
is the number of parameters.
yield 88%. ΛM ) 4 Ω-1 cm2 mol-1 1H NMR: δ 4.30 (m, 4H,
.
4.23 (m, 2H, C5H4), 4.76 (m, 4H, C5H4), 5.03 (m, 4H, C5H4),
7.2-7.6 (m, 40H, Ph) ppm. 31P{1H} NMR (room tempera-
ture): δ 25.0 (br, 4P, dppf). 31P{1H} NMR (-55 °C): δ 29.1
(br, 2P, dppf), 28.7 (br, 2P, dppf) ppm. 19F NMR (room
temperature): δ -123.8 (m, 4F, o-F, C6F5), -130.0 (m, br, 4F,
o-F, SC6F5), -160.0 (m, 10F, m-F, C6F5 + SC6F5 + p-F, C6F5),
-153.6 (t, 2F, p-F, SC6F5, J (FF) ) 21.15 Hz).
C5H4), 4.67 (m, 4H, C5H4), 7.3-7.6 (m, 20H, Ph) ppm. 31P{1H}
NMR: δ 25.2 (s, 2P, dppf) ppm. 19F NMR: δ -132.2 (m, 4F,
3
o-F), -161.7 (m, 4F, m-F), -156.6 (t, 2F, p-F, J (FF) ) 21.36
1
Hz) ppm. Complex 10: yield 70%. ΛM ) 32 Ω-1 cm2 mol-1. H
NMR: δ 4.41 (m, 4H, C5H4), 4.57 (m, 4H, C5H4), 7.3-7.7 (m,
20H, Ph) ppm. 31P{1H} NMR: δ 32.4 (s, 2P, dppf) ppm. 19F
NMR: δ -131.1 (m, 4F, o-F), -162.6 (m, 4F, m-F), -158.8 (t,
Cr ysta l Str u ctu r e Deter m in a tion s. The crystals were
mounted in inert oil on glass fibers and transferred to the cold
gas stream of a Siemens P4 diffractometer equipped with an
Oxford (6) or Siemens LT-2 (11) low-temperature attachment.
Data were collected using monochromated Mo KR radiation
(λ ) 0.710 73 Å). The scan type was θ-2θ (6) or ω (11). Cell
constants were refined from setting angles of ca. 60 reflections
in the 2θ range 10-25°. Absorption corrections were applied
on the basis of ψ-scans. Structures were solved by direct
methods and refined on F2 using the programs SHELXL-93
and SHELXL-97.20 All non-hydrogen atoms except C and O
atoms of 11 were refined anisotropically. Hydrogen atoms were
included using a riding model. A systems of restraints to light-
atom displacement-factor components and local ring symmetry
was used. The structure of complex 11 contains 2.5 indepen-
dent dichloromethane molecules, one of which is badly resolved
(C atom not located). One perchlorate is also badly resolved.
Further details are given in Table 3.
3
2F, p-F, J (FF) ) 21.16 Hz) ppm.
[Au 2(µ-SC6F 5)(µ-d p p f)]ClO4 (11). To a solution of [Au2-
(SC6F5)2(µ-dppf)] (0.136 g, 0.1 mmol) in dichloromethane (20
mL) was added AgClO4 (0.021 g, 0.1 mmol), and the mixture
was stirred for 1 h protected from light. Then the white
precipitate of [Ag(SC6F5)]n was filtered off and the solution
concentrated to ca. 5 mL. Addition of diethyl ether gave an
orange solid of complex 11. Yield: 86%. ΛM ) 128 Ω-1 cm2
mol-1. Anal. Found: C, 38.16; H, 1.86; S, 3.03. Calcd for C40H28
-
1
Au2ClF5FeO4P2S: C, 38.53; H, 2.26; S, 2.57. H NMR: δ 4.26
(m, 4H, C5H4), 4.63 (m, 4H, C5H4), 7.3-7.6 (m, 20H, Ph) ppm.
31P{1H} NMR: δ 29.6 (s, 2P, dppf) ppm. 19F NMR: δ -129.8
3
(m, 2F, o-F), -159.9 (m, 2F, m-F), -153.8 (t, F, p-F, J (FF) )
21.36 Hz) ppm.
[Au 5(C6F 5)2(µ3-SC6F 5)2(µ-d p p f)2](ClO4)3 (12). To a solution
of [Au2(µ-SC6F5)(µ-dppf)]ClO4 (0.249 g, 0.2 mmol) in dichlo-
romethane (20 mL) was added a diethyl ether solution (20 mL)
of [Au(C6F5)2(OEt2)2]ClO4 (0.078 g, 0.1 mmol) and the mixture
stirred for 15 min. Then evaporation of the solvent to ca. 5
mL and addition of hexane afforded complex 12 as an orange
solid. Yield: 90%. ΛM ) 256 Ω-1 cm2 mol-1. Anal. Found: C,
35.09; H, 1.94; S, 2.09. Calcd for C92H56Au5Cl3F20Fe2O12P4S2:
Ack n ow led gm en t. We thank the Direccio´n General
de Investigacio´n Cient´ıfica y Te´cnica (No. PB97-1010-
C02-01), the Caja de Ahorros de la Inmaculada (No.
CB4/98), and the Fonds der Chemischen Industrie for
financial support.
1
C, 35.37; H, 1.81; S, 2.05. H NMR (room temperature): δ 4.3
1
(m, br, 16H, C5H4), 7.2-7,6 (m, 40H, Ph). H NMR (-55 °C):
δ 3.65 (m, 2H, C5H4), 3.67 (m, 2H, C5H4), 4.21 (m, 2H, C5H4),
Su p p or tin g In for m a tion Ava ila ble: Two X-ray crystal-
lographic files, in CIF format, for 6 and 11. This material is
available free of charge via the Internet at http://pubs.acs.org.
(20) Sheldrick, G. M. SHELXL-93 and SHELXL-97, Program for
Crystal Structure Refinement; University of Go¨ttingen, Go¨ttingen,
Germany, 1993 and 1997.
OM9901372