Synthesis and reactivity of the first (hydrosulfido)gold(III) complex. Crystal structure of the derivatives NBu4[{Au(C6F5)3}2SR] with the isolobal fragments R = H, AuPPh3, AgPPh3

Article abstract of DOI:10.1021/om971111i

The treatment of NBu₄[AuBr(C₆F₅)₃] with NaSH affords the (hydrosulfido)gold(III) complex NBu₄[Au(C₆F₅)₃SH]. The latter compound reacts with [Au(C₆F₅

Full text of DOI:10.1021/om971111i

Organometallics 1998, 17, 1617-1621
1617
Syn th esis a n d Rea ctivity of th e F ir st
(Hyd r osu lfid o)gold (III) Com p lex. Cr ysta l Str u ctu r e of
th e Der iva tives NBu 4[{Au (C6F 5)3}2SR] w ith th e Isoloba l
†
F r a gm en ts R ) H, Au P P h 3, AgP P h 3
Fernando Canales,‡ Silvia Canales,‡ Olga Crespo,‡ 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, 50009 Zaragoza, Spain, and Institut fu¨r Anorganische und
Analytische Chemie der Technischen Universita¨t, Postfach 3329,
D-38023 Braunschweig, Germany
Received December 17, 1997
The treatment of NBu4[AuBr(C6F5)3] with NaSH affords the (hydrosulfido)gold(III) complex
NBu4[Au(C6F5)3SH]. The latter compound reacts with [Au(C6F5)3OEt2] to give the dinuclear
species NBu4[{Au(C6F5)3}2SH]. The isolobal analogy between H, AuPPh3, and AgPPh3 can
be recognized in the complexes NBu4[{Au(C6F5)3}2S(MPPh3)] (M ) Au, Ag) synthesized by
reaction of NBu4[{Au(C6F5)3}2SH] with [Au(OClO3)(PPh3)] or [Ag(O3SCF3)(PPh3)] in the
presence of Na2CO3. The structures of complexes NBu4[{Au(C6F5)3}2SR] (R ) H, AuPPh3,
AgPPh3) have been established by X-ray diffraction studies and show a trigonal-pyramidal
geometry at sulfur with no short gold-gold or gold-silver interactions between the metallic
centers.
In tr od u ction
retical studies when considered as a correlation effect,
strengthened by relativistic effects.10-13 We have also
investigated this type of interaction between gold(I) and
gold(III) centers, showing it to be possible, although
weaker than a gold(I)-gold(I) interaction.9
There is much current interest in the chemistry of
transition-metal hydrosulfido complexes, mainly be-
cause these are useful in understanding many catalytic
processes such as hydrogenation and hydrodesulfura-
tion.1,2 These species are still quite rare. (Hydrosulfi-
do)gold complexes, for example, are very poorly repre-
sented; to the best of our knowledge only the gold(I)
compounds [N(PPh3)2][Au(SH)2]3 and Q[AuR(SH)] (R )
C6F5, 2-(NO2)C6H4, 2,4,6-(NO2)3C6H2)4 have been re-
ported and no gold(III) derivatives have been described
thus far.
We are currently studying gold complexes with bridg-
ing sulfido ligands and have reported on the ability of
[S(AuPR3)2] and [S{Au2(µ-dppf)}] to coordinate further
gold(I) or gold(III) centers. These polynuclear deriva-
tives show weak metal-metal interactions between the
closed-shell d10 metal centers, termed aurophilic
attractions,5-9 that cannot be explained in terms of the
classical theory of chemical bonding, but only in theo-
In this paper we have used a different approach to
synthesize sulfur-centered gold complexes: we have
prepared the convenient gold(III) starting material
NBu4[Au(C6F5)3(SH)], which represents the first ex-
ample of a (hydrosulfido)gold(III) derivative. This
complex can be used to coordinate further metallic
fragments. In some of the complexes described here it
is possible to envisage the isolobal analogy existing
between the hydrogen atom and the fragments AuPR3
and AgPR3.
Resu lts a n d Discu ssion
The reaction of NBu4[AuBr(C6F5)3] with NaSH in an
acetone/water mixture gives after workup the (hydro-
sulfido)gold(III) derivative NBu4[Au(C6F5)3SH] (1) in
high yield (96%) (see Scheme 1). The IR spectrum of 1
is very similar to that of the starting material, with the
exception of a weak band at 313 cm-1 assignable to the
vibration ν(Au-S); also present are the absorptions of
the pentafluorophenyl groups bonded to a gold(III)
center at 1507 (vs) and 966 (vs) cm-1. The IR-active
† Dedicated to Professor P. Royo on the occasion of his 60th birthday.
‡ Universidad de Zaragoza-CSIC.
§ Technische Universita¨t Braunschweig.
(1) Angelici, R. J . Acc. Chem. Res. 1988, 21, 387 and references
therein.
(2) Rakowski-Dubois, M. Chem. Rev. 1989, 89, 2 and references
therein.
(3) Vicente, J .; Chicote, M. T.; Gonza´lez-Herrero, P.; J ones, P. G.;
Ahrens, B. Angew. Chem., Int. Ed. Engl. 1994, 33, 1852.
(4) Vicente, J .; Chicote, M. T.; Gonza´lez-Herrero, P.; Gru¨nwald, C.;
J ones, P. G. Angew. Chem., Int. Ed. Engl. 1994, 33, 1852.
(5) Canales, F.; Gimeno, M. C.; J ones, P. G.; Laguna, A. Angew.
Chem., Int. Ed. Engl. 1994, 33, 769.
(6) Canales, F.; Gimeno, M. C.; Laguna, A.; Villacampa, M. D. Inorg.
Chim. Acta 1996, 244, 95.
(7) Canales, F.; Gimeno, M. C.; Laguna, A.; J ones, P. G. J . Am.
Chem. Soc. 1996, 118, 4839.
(8) Canales, F.; Gimeno, M. C.; Laguna, A.; J ones, P. G. Organo-
metallics 1996, 15, 3412.
(9) Calhorda, M. J .; Canales, F.; Gimeno, M. C.; J ime´nez, J .; J ones,
P. G.; Laguna, A.; Veiros, L. F. Organometallics 1997, 17, 3837.
(10) Kaltsoyannis, N. J . Chem. Soc., Dalton Trans. 1997, 1.
(11) Pyykko¨, P. Chem. Rev. 1997, 97, 597.
(12) Pyykko¨, P.; Runeberg, N.; Mendizabal, F. Chem. Eur. J . 1997,
3, 1451.
(13) Pyykko¨, P.; Mendizabal, F. Chem. Eur. J . 1997, 3, 1458.
S0276-7333(97)01111-4 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 03/18/1998

1618 Organometallics, Vol. 17, No. 8, 1998
Canales et al.
a
Sch em e 1
F igu r e 1. Structure of the anion of complex 2 in the
crystal. Displacement parameter ellipsoids represent 50%
probability surfaces. The H atoms (except SH) are omitted
for clarity.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 2
a
Legend: (i) [Au(C6F5)3(OEt2)]; (ii) [Au(OClO3)PPh3] +
Na2CO3; (iii) [Ag(O3SCF3)PPh3] + Na2CO3.
Au(1)-C(1)
Au(1)-C(21)
Au(2)-C(31)
Au(2)-C(51)
2.042(13)
2.080(14)
2.051(13)
2.102(14)
Au(1)-C(11)
Au(1)-S
2.064(14)
2.390(3)
2.086(14)
2.367(3)
band corresponding to the ν(SH) mode that usually
appears in the range 2300-2600 cm-1 is not observed;
its weakness is a common feature of most SH complexes.
Au(2)-C(41)
Au(2)-S
1
The H NMR spectrum shows the signals assigned to
C(1)-Au(1)-C(11)
89.4(5)
C(1)-Au(1)-C(21)
C(1)-Au(1)-S
88.6(5)
175.8(4)
89.7(4)
C(11)-Au(1)-C(21) 177.5(5)
the protons of the NBu4 group and a singlet at -0.45
ppm, which corresponds to the SH proton. In the 19F
NMR spectrum the typical pattern of a tris(pentafluo-
rophenyl)gold(III) unit appears; each pentafluorophenyl
unit presents two multiplets and one triplet for the
different fluorine nuclei; thus, six resonances appear in
a 2:1 ratio because of the equivalence of the mutually
trans C6F5 groups.
In the negative liquid secondary ion mass spectrum
(LSIMS-) the anionic peak [Au(C6F5)3SH]- appears at
m/z 731 (60%), the peak assigned to [Au(C6F5)4]- ap-
pears at m/z 865, and the association peaks [{Au(C6F5)}-
{Au(C6F5)3}SH]- and [{Au(C6F5)3}2SH]- appear at m/z
1095 and 1429, respectively.
C(11)-Au(1)-S
92.3(4)
C(21)-Au(1)-S
C(31)-Au(2)-C(41) 86.9(5)
C(41)-Au(2)-C(51) 176.5(5)
C(31)-Au(2)-C(51) 91.0(5)
C(31)-Au(2)-S
C(51)-Au(2)-S
173.7(4)
89.6(4)
118.8(10)
C(41)-Au(2)-S
Au(2)-S-Au(1)
C(6)-C(1)-Au(1)
92.1(4)
113.76(13) C(2)-C(1)-Au(1)
122.7(10) C(12)-C(11)-Au(1) 122.6(11)
C(16)-C(11)-Au(1) 123.9(11) C(26)-C(21)-Au(1) 121.7(11)
C(22)-C(21)-Au(1) 120.6(11) C(36)-C(31)-Au(2) 126.3(10)
C(32)-C(31)-Au(2) 117.9(10) C(42)-C(41)-Au(2) 122.1(11)
C(46)-C(41)-Au(2) 120.9(12) C(52)-C(51)-Au(2) 124.5(11)
C(56)-C(51)-Au(2) 118.2(11)
wider than that expected for an ideal tetrahedron
(113.76(13)°). The Au-S distances, 2.390(3) and 2.367(3)
Å, are very similar to those found in other gold(III)
complexes triply bonded to a sulfur atom such as [S(Au2-
dppf){Au(C6F5)3}]9 (dppf ) 1,1′-bis(diphenylphosphino)-
ferrocene) (2.374(4) Å) or [{S(Au2dppf)}2{Au(C6F5)2}](CF3-
SO3)9 (2.387(4), 2.397(4) Å), but they are also of the same
order as those found in complexes with a µ4-sulfur
moiety such as [S(Au2dppf){Au(C6F5)3}2]8 (2.380(3),
2.385(3) Å) and [S(AuPPh3)2{Au(C6F5)3}2].8 The Au-C
bond lengths vary depending on the position of the C6F5
group; the shortest distances correspond to the carbon
atoms trans to the sulfur atom, 2.042(13) and 2.051(13)
Å, and the others are typical values for tris(pentafluo-
rophenyl)gold(III) complexes. The SH hydrogen is
directed toward a chlorine atom of the dichloro-
methane molecule; this may represent a weak S-H‚‚‚Cl
hydrogen bond (H‚‚‚Cl ) 2.66 Å, S‚‚‚Cl ) 3.79 Å,
S-H‚‚‚Cl ) 143°).
This indicated to us that the hydrosulfido ligand
bonded to gold(III) could easily coordinate other metallic
fragments. Taking this into account, we have studied
the reaction of 1 with [Au(C6F5)3OEt2] in the molar ratio
1:1. The weakly coordinated ether molecule is displaced
by the hydrosulfido group, and the complex NBu4-
[{Au(C6F5)3}2SH] (2) can be isolated.
The 1H and 19F NMR spectra of 2 have patterns
similar to those of 1, although with a different chemical
1
shift. The SH proton is not observed in the H NMR
spectrum, perhaps because it is overlapped by the NBu4
protons. In the LSIMS- the anionic peak appears at
m/z 1429 (42%).
The structure of complex 2 has been determined by
X-ray diffraction studies of its dichloromethane solvate;
the anion is shown in Figure 1, with a selection of bond
lengths and angles in Table 1. The hydrogen atom of
the SH- ligand could be located with reasonable cer-
tainty (see below), and the geometry can be considered
as triangular pyramidal at sulfur, or tetrahedral if we
take into account the lone pair. The gold(III)-gold(III)
distance, 3.984(1) Å, is too long to be considered an
interaction; furthermore, the Au-S-Au angle is even
It is well-known that the AuPR3 group is isolobal with
the hydrogen atom and mostly uses the 6s orbital of gold
for bonding. This isolobal relationship explains the
often close structural analogy between various homo-
and heteronuclear compounds containing AuPR3 groups
and those of the related hydrido derivatives. This
isolobal analogy also extends to the AgPPh3 group; thus,

The First (Hydrosulfido)gold(III) Complex
Organometallics, Vol. 17, No. 8, 1998 1619
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 3
Au(1)-C(21)
Au(1)-C(1)
Au(2)-C(41)
Au(2)-C(31)
Au(3)-P
2.05(2)
2.07(2)
2.00(2)
2.05(2)
2.250(5)
Au(1)-C(11)
Au(1)-S
2.05(2)
2.374(5)
2.04(2)
2.374(5)
2.303(5)
Au(2)-C(51)
Au(2)-S
Au(3)-S
C(21)-Au(1)-C(11)
C(11)-Au(1)-C(1)
C(11)-Au(1)-S
89.3(7)
90.2(7)
176.5(5)
89.4(6)
C(21)-Au(1)-C(1)
C(21)-Au(1)-S
C(1)-Au(1)-S
C(41)-Au(2)-C(31)
C(41)-Au(2)-S
C(31)-Au(2)-S
Au(3)-S-Au(1)
Au(1)-S-Au(2)
C(81)-P-Au(3)
C(2)-C(1)-Au(1)
173.4(5)
93.6(5)
87.1(5)
87.8(6)
172.4(3)
89.8(5)
107.4(2)
108.4(2)
113.3(6)
125.4(14)
C(41)-Au(2)-C(51)
C(51)-Au(2)-C(31) 176.3(6)
C(51)-Au(2)-S
P-Au(3)-S
Au(3)-S-Au(2)
C(61)-P-Au(3)
C(71)-P-Au(3)
C(6)-C(1)-Au(1)
92.6(5)
173.6(2)
113.0(2)
113.3(5)
112.6(6)
120.0(13) C(12)-C(11)-Au(1) 122.5(13)
C(16)-C(11)-Au(1) 123.5(13) C(26)-C(21)-Au(1) 125.4(11)
C(22)-C(21)-Au(1) 121.1(10) C(32)-C(31)-Au(2) 121.4(10)
C(36)-C(31)-Au(2) 125.3(10) C(42)-C(41)-Au(2) 121.5(10)
C(46)-C(41)-Au(2) 127.5(11) C(56)-C(51)-Au(2) 123.2(11)
C(52)-C(51)-Au(2) 122.0(10)
F igu r e 2. Perspective view of the anion of complex 3.
Displacement parameter ellipsoids represent 50% prob-
ability surfaces. H atoms are omitted for clarity.
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 4
Au(1)-C(11)
Au(1)-C(21)
Au(2)-C(41)
Au(2)-C(31)
Ag-P
2.038(8)
2.058(7)
2.046(7)
2.062(7)
2.355(2)
1.811(8)
1.823(9)
Au(1)-C(1)
Au(1)-S
Au(2)-C(51)
Au(2)-S
Ag-S
2.050(8)
2.374(2)
2.058(7)
2.361(2)
2.357(2)
1.819(8)
P-C(61)
P-C(71)
P-C(81)
C(11)-Au(1)-C(1)
C(1)-Au(1)-C(21)
C(1)-Au(1)-S
91.1(3)
173.5(3)
87.7(2)
87.9(2)
C(11)-Au(1)-C(21)
C(11)-Au(1)-S
C(21)-Au(1)-S
C(41)-Au(2)-C(31)
C(41)-Au(2)-S
C(31)-Au(2)-S
88.5(3)
177.8(2)
92.9(2)
90.0(2)
172.1(2)
92.2(2)
111.84(8)
108.23(7)
105.6(3)
112.3(2)
113.3(2)
119.5(6)
C(41)-Au(2)-C(51)
C(51)-Au(2)-C(31) 177.0(3)
C(51)-Au(2)-S
P-Ag-S
89.6(2)
171.78(7) Ag-S-Au(2)
107.79(8) Au(2)-S-Au(1)
105.6(3)
106.1(3)
113.3(2)
125.4(7)
120.0(8)
Ag-S-Au(1)
C(61)-P-C(71)
C(71)-P-C(81)
C(71)-P-Ag
C(61)-P-C(81)
C(61)-P-Ag
C(81)-P-Ag
C(2)-C(1)-Au(1)
F(1)-C(2)-C(1)
C(6)-C(1)-Au(1)
F igu r e 3. Structure of the anion of complex 4 in the
crystal. Displacement parameter ellipsoids represent 50%
probability surfaces. The H atoms are omitted for clarity.
C(12)-C(11)-Au(1) 122.5(6)
C(42)-C(41)-Au(2) 118.8(5)
C(52)-C(51)-Au(2) 121.4(5)
C(16)-C(11)-Au(1) 122.8(6)
C(46)-C(41)-Au(2) 125.0(5)
C(56)-C(51)-Au(2) 124.1(5)
C(66)-C(61)-P
121.4(6)
we have synthesized the complexes NBu4[{Au(C6F5)3}2-
SR] (R ) AuPPh3 (3), AgPPh3 (4)), which are isolobal
with complex 2.
C(62)-C(61)-P
117.1(6)
plexes are isostructural and show the expected trigonal-
pyramidal geometry with the sulfur at the vertex lying
0.78 (3) or 0.79 (4) Å out of the plane of the three
metallic centers. The gold(III) centers have a very
regular square planar geometry with angles that range
from 87.8(6) to 92.6(5)° in 3 and from 87.7(2) to 92.9(2)°
in 4, whereas the gold(I) or silver(I) has a distorted
linear geometry, S-Au(3)-P ) 173.6(2)° and S-Ag-P
) 171.78(7)°.
It is worth comparing these structures to those which
have a sulfido ligand triply bridged to three gold(I)
centers, [S(AuPR3)3]+, and to two gold(I) and one gol-
d(III) center, [S(Au2dppf){Au(C6F5)3}]. In complexes of
the type [S(AuPR3)]+ there are short Au‚‚‚Au contacts
of ca. 3 Å and usually the molecules are associated in
pairs through intermolecular gold-gold interactions. In
[S(Au2dppf)2{Au(C6F5)3}] there is a short intramolecular
gold(I)-gold(I) contact and two different gold(I)-gold-
(III) distances (3.404(1) and 3.759(1) Å); in [{S(Au2-
dppf)}2{Au(C6F5)2}](CF3SO3), which has the same type
of structure, the shorter Au(I)-Au(III) distance de-
Complexes 3 and 4 are white solids, stable to moisture
and air. They behave as 1:1 electrolytes in acetone. In
the IR spectra the bands arising from the pentafluo-
rophenyl groups, the PPh3 ligand, and the vibration
ν(Au-S) appear. The vibration ν(Ag-S) is not observed,
possibly because it is too weak or is below the instru-
mental limit of 200 cm-1. In the 31P{1H} NMR spectra
the phosphorus bonded to gold appears as a singlet,
whereas that bonded to silver appears as a broad signal
at room temperature that sharpens into two doublets
because of the coupling with the silver nuclei 107Ag and
109Ag.
The negative liquid secondary ion mass spectra of
complexes 3 and 4 show the anionic peaks at m/z 1887
(3; 23%) and 1799 (4; 7%) with coincident experimental
and calculated isotopical distribution.
The crystal structures of complexes 3 and 4 have been
established by X-ray diffraction, and the anions are
shown in Figures 2 and 3 with selected bond lengths
and angles in Tables 2 and 3, respectively. The com-

1620 Organometallics, Vol. 17, No. 8, 1998
Canales et al.
Ta ble 4. Deta ils of Da ta Collection a n d Str u ctu r e
creases to 3.2195(8) Å, a value that is of the same order
as the longest gold(I)-gold(I) interactions in this type
of complex and shows that gold(I)-gold(III) interactions,
although weaker, are also possible. In complexes 3 and
4, in contrast, there are no short metal-metal distances;
in 3 the Au(I)-Au(III) distances are 3.770(1) and
3.900(1) Å, which, although they follow the pattern
previously mentioned, are too long to be considered as
interactions; the gold(III)-gold(III) distance is 3.852(1)
Å. The corresponding Ag-Au(III) distances in 4 are
longer, 3.882(1) and 3.907(1) Å, but the Au(III)-Au(III)
distance is very similar, 3.836(1) Å.
Consistent with the long metal-metal distances, the
Au-S-Au or Ag-S-Au angles are close to the ideal
values for a tetrahedron. The AuIII-S distances are
2.374(5) Å (×2) in 3 and 2.374(2) and 2.357(2) Å in 4,
values that are shorter than those found in the starting
material. The AuI-S bond length is 2.303(5) Å, and the
Ag-S length is 2.357(2) Å, which is in accordance with
the observations14-16 made by Schmidbaur et al. that
the covalent radius of gold is smaller than that of silver,
as was anticipated on the basis of data obtained in
theoretical treatments including relativistic effects.
Refin em en t for Com p lexes 2-4
compd
chem formula
2‚CH2Cl2
C53H39Au2-
Cl2F30NS
colorless
prism
3‚CH2Cl2
C71H53Au3-
Cl2F30NPS
colorless
prism
4‚CH2Cl2
C71H53AgAu2-
Cl2F30NPS
colorless
cryst habit
tablet
cryst size/mm
0.25 × 0.20 × 0.15 × 0.15 × 0.50 × 0.25 ×
0.20
0.11
triclinic
P1h
0.10
triclinic
P1h
cryst syst
space group
a/Å
b/Å
c/Å
R/deg
â/deg
γ/deg
V/Å3
monoclinic
P21/c
12.3740(10)
18.217(2)
26.363(3)
12.442(2)
13.084(3)
23.125(4)
87.96(2)
81.80(2)
85.499(14)
3713.5(12)
2
12.448(2)
13.114(2)
23.161(3)
86.968(10)
81.152(10)
85.320(10)
3720.3(10)
2
98.848(7)
5872.0(10)
4
Z
D
calcd/Mg m-3
1.987
1.981
1.898
Mr
F(000)
1756.75
3368
2214.97
2116
2125.88
2052
T/°C
-100
-100
-100
2θmax/deg
µ(Μo KR)/mm-1
transmissn
no. of rflns measd 8796
no. of unique rflns 7517
45
45
50
5.25
0.705-0.919
6.151
4.434
0.682-0.960
10 260
9720
0.074
0.068
0.145
9697
892
788
0.696-0.982
13 130
13 081
0.020
0.040
0.095
13 081
999
886
0.895
2.103
Rint
0.07
0.052
0.10
7505
794
760
1.051
0.931
Ra(F, F > 4σ(F))
Rw (F2, all rflns)b
no. of rflns used
no. of params
no. of restraints
Sc
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 and H 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 in CDCl3 on a Varian Unity 300 spectrometer and a
Bruker ARX 300 spectrometer. Chemical shifts are cited
relative to SiMe4 (1H, external), CFCl3 (19F, external), and 85%
H3PO4 (31P, external).
1.046
2.24
max ∆F/e Å-3
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
the number of parameters.
o-F), -122.6 (m, 2F, o-F), -164.1 (m, 4F, m-F), -164.2 (m, 2F,
m-F), -161.1 [t, 2F, p-F, 3J (FF) ) 19.34 Hz], -161.2 [t, 1F,
3
p-F, J (FF) ) 19.29 Hz] ppm.
Ma ter ia ls. The starting materials NBu4[AuBr(C6F5)3]17
and [Au(C6F5)3OEt2]18 were prepared by published procedures.
[Au(OClO3)PPh3] was prepared from [AuCl(PPh3)]19 and Ag-
ClO4 in dichloromethane, and [Ag(O3SCF3)(PPh3)] was ob-
tained from Ag(O3SCF3) and PPh3 in dichloromethane.
Sa fety Note. Caution! Perchlorate salts of metal com-
plexes 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. NBu 4[Au (C6F 5)3SH] (1). To a solution of
NBu4[AuBr(C6F5)3] (0.1 mmol; 0.102 g) in an acetone/water
mixture (20/5 mL) was added NaSH (1 mmol, 0.056 g). The
solution was stirred for 3 h, and then the solvent was
evaporated to ca. 5 mL. The resulting solid was filtered off
and washed several times with water. The solid was dissolved
in dichloromethane and the solution filtered over MgSO4. The
resulting solution was concentrated to ca. 5 mL, and addition
of hexane gave a white solid of 1. Yield: 96%. ΛM ) 121 Ω-1
cm2 mol-1. Anal. Found: C, 41.44; H, 3.31; N, 1.46; S, 3.21.
Calcd for C34H37AuF15NS: C, 41.94; H, 3.73; N, 1.44; S, 3.29.
1H NMR: δ -0.45 (s) (SH) ppm. 19F NMR: δ -120.9 (m, 4F,
NBu 4[{Au (C6F5)3}2SH] (2). To a solution of NBu4[Au(C6F5)3-
SH] (0.1 mmol, 0.097 g) in dichloromethane (20 mL) was added
NBu4[AuBr(C6F5)3] (0.1 mmol, 0.102 g), and the solution was
stirred for 3 h. The solvent was evaporated to ca. 5 mL, and
addition of hexane afforded a white solid of 2. Yield: 90%.
ΛM ) 111.5 Ω-1 cm2 mol-1. Anal. Found: C, 37.16; H, 1.80;
N, 0.73; S, 2.21. Calcd for C52H37Au2F30NS: C, 37.36; H, 2.23;
N, 0.84; S, 1.92. 19F NMR: δ -121.4 (m, 8F, o-F), -122.0 (m,
4F, o-F), -162.1 (m, 8F, m-F), -162.4 (m, 4F, m-F), -147.8 [t,
4F, p-F, 3J (FF) ) 19.29 Hz], -158.0 [t, 2F, p-F, 3J (FF) ) 19.98
Hz] ppm.
NBu 4[{Au (C6F 5)3}2S(MP P h 3)] (M ) Au (3), Ag (4)). To
a dichloromethane (20 mL) solution of 2 (0.1 mmol, 0.167 g)
was added [Au(OClO3)PPh3] (0.1 mmol, 0.056 g) or [Ag(O3-
SCF3)PPh3] (0.1 mmol, 0.052 g) and excess Na2CO3 (2 mmol,
0.212 g), and the suspension was stirred for 1 h. The solid
sodium carbonate was filtered off and the solvent evaporated
to ca. 5 mL. Addition of hexane (15 mL) led to white solid 3 or
4. Complex 3: yield 75%. ΛM ) 107 Ω-1 cm2 mol-1
Found: C, 39.44; H, 1.98; N, 0.51; S, 1.94. Calcd for
. Anal.
C
70H52Au3F30NPS: C, 39.47; H, 2.41; N, 0.66; S, 1.51. 31P-
{1H} NMR, δ 36.5 ppm. 19F: δ -121.1 (m, 8F, o-F), -121.7
(m, 4F, o-F), -163.3 (m, 8F, m-F), -163.4 (m, 4F, m-F), -160.2
[t, 4F, p-F, 3J (FF) ) 19.98 Hz], -159.9 [t, 2F, p-F, 3J (FF) )
(14) Bayler, A.; Schier, A.; Bowmaker, G. A.; Schmidbaur, H. J . Am.
Chem. Soc. 1996, 118, 7006.
(15) Bowmaker, G. A.; Schmidbaur, H.; Kru¨ger, S.; Ro¨sch, M. Inorg.
Chem. 1997, 36, 1754.
(16) Tripathi, U. M.; Bauer, A.; Schmidbaur, H. J . Chem. Soc.,
Dalton Trans. 1997, 2865.
(17) Uso´n, R.; Laguna, A.; Vicente, J . J . Organomet. Chem. 1997,
131, 71.
19.99 Hz] ppm. Complex 4: Yield 51%. ΛM 114 Ω-1 cm2 mol-1
.
Anal. Found: C, 40.69; H, 2.47; N, 0.68; S, 1.55. Calcd for
C
70H52AgAu2F30NPS: C, 40.45; H, 2.57; N, 0.70; S, 1.77. 19F:
δ -120.1 (m, 8F, o-F), -121.8 (m, 4F, o-F), -163.3 (m, 8F,
3
m-F), -163.3 (m, 4F, m-F), -160.4 [t, 4F, p-F, J (FF) ) 20.6
(18) Uso´n, R.; Laguna, A.; Laguna, M.; J ime´nez, J .; Durana, E.
Inorg. Chim. Acta 1990, 168, 89.
(19) Uso´n, R.; Laguna, A. Inorg. Synth. 1982, 21, 71.
3
Hz], -160.3 [t, 2F, p-F, J (FF) ) 20.2 Hz] ppm.
Cr ysta l Str u ctu r e Deter m in a tion s. The crystals were

The First (Hydrosulfido)gold(III) Complex
Organometallics, Vol. 17, No. 8, 1998 1621
mounted in inert oil on glass fibers and transferred to the cold
gas stream of a Siemens P4 diffractometer equipped with an
Oxford (2, 3) or Siemens LT-2 (4) low-temperature attachment.
Data were collected using monochromated Mo KR radiation
(λ ) 0.710 73 Å). The scan type was θ-2θ (2, 3) or ω (4). Cell
constants were refined from setting angles of ca. 60 reflections
in the range 2θ ) 10-25°. Absorption corrections were applied
on the basis of ψ-scans. Structures were solved by direct
methods and refined on F2 using the program SHELXL-93.20
All ordered non-hydrogen atoms were refined anisotropically
(2, 4). For complex 3, with a weakly diffracting crystal, the
carbon and nitrogen atoms of the NBu4 cation were refined
isotropically. Complexes 3 and 4 crystallized with a very ill-
defined dichloromethane molecule, the carbon atom of which
could not be located; the major residual electron density in
these structures is found near the chlorine atoms of the
dichloromethane. Hydrogen atoms were included using a
riding model. A system of restraints to light-atom displace-
ment-factor components and local ring symmetry was used.
Further details are given in Table 4. Special features of
refinement for 2: Despite apparently reasonable data, the H
atom of the SH ligand could not at first be located. Only when
two butyl groups of the cation had been refined using a 2-fold
disorder model (with appropriate restraints) could a peak of
0.73 e/Å3 (the fifth largest at that stage) be located in a suitable
position. It was refined using a restrained S-H bond length
of 1.33(2) Å.
Ack n ow led gm en t. We thank the Direccio´n General
de Investigacio´n Cient´ıfica y Te´cnica (No. PB94-0079),
the Caja de Ahorros de la Inmaculada (No. CB8/97), and
the Fonds der Chemischen Industrie for financial sup-
port.
Su p p or tin g In for m a tion Ava ila ble: Tables giving crys-
tal data and structure refinement details, positional and
thermal parameters, and bond distances and angles for 2-4
(34 pages). Ordering information is given on any current
masthead page.
(20) Sheldrick, G. M.; SHELXL-93, Program for Crystal Structure
Refinement; University of Go¨ttingen, Go¨ttingen, Germany, 1993.
OM971111I