Synthesis and Reactivity of Heteroleptic Complexes of Gold with 2-Thioxo-1,3-dithiole-4,5-dithiolate (dmit). X-ray Structure of [Au2(μ-dmit)(PPh3)2], (NBu4)[Au(dmit)(PPh3)], and (PPN)[Au(dmit)(C6F5)2]

Article abstract of DOI:10.1021/ic950893+

The reactions of Na₂dmit (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) with AuCIL in 1:2 ratios lead to [Au₂(dmit)L₂] [L = PPh₃ (1), PPh₂Me (2), PPhMe₂ (3), PMe₃ (4), CH₂PPh₃ (5), CH₂PPh₂Me (6), CH₂PPhMe₂ (7)]. Complexes 1, 2, and 5 react further with equimolecular amounts of [AuL(tht)]ClO₄ (tht = tetrahydrothiophene), affording trinuclear complexes [Au₃(dmit)L₃]ClO₄ (8-10). When the reactions of Na₂dmit with AuCIL are carried out in 1:1 ratios and in the presence of NBu₄Br, mononuclear tricoordinated gold(I) complexes NBu₄[Au(dmit)L] [L = PPh₃ (11), PPh₂Me (12), PMe₃ (13)] are obtained. Other anionic derivatives such as (PPN)₂[Au₂(dmit)X₂] [X = C₆F₅ (14), Cl (15a), Br (15b)] can be obtained either by reaction of Na₂dmit with Q[Au(C₆F₅)X] in 1:2 ratio or by addition of (PPN)X to the recently reported [Au₂(dmit)(AsPh₃)]. Oxidative reactions of 11,12, and 14 or 15b with excess (TTF)₃(BF₄)₂ afford (TTF) ₂[Au(dmit)₂] (16), (TTF)[Au₂(dmit)(C₆F₅)₂] (17), and (TTF)₃[Au₂(dmit)-Br₂] (18), respectively. Reaction of complex 14 with TCNQ gives the anionic gold(III) complex [Au(dmit)(C₆F₅)₂]^- (19). Electrical conductivities of these complexes at room temperature in compacted pellets are 2 × 10^-3 (16), 7 × 10^-5 (17), and 2 × 10^-2 (18) S·cm^-1. Electrocrystallization of 1 and 11 affords [Au₂(dmit)₂(PPh₃)] (20) and the known NBu₄[Au(dmit)₂], respectively. X-ray structure determinations were performed for complexes 1,11, and 19b.

Full text of DOI:10.1021/ic950893+

Inorg. Chem. 1996, 35, 2995-3000
2995
Synthesis and Reactivity of Heteroleptic Complexes of Gold with
2-Thioxo-1,3-dithiole-4,5-dithiolate (dmit). X-ray Structure of [Au2(µ-dmit)(PPh3)2],
(NBu4)[Au(dmit)(PPh3)], and (PPN)[Au(dmit)(C6F5)2]
Elena Cerrada,† Peter G. Jones,‡ Antonio Laguna,† and Mariano Laguna*,†
Departamento de Qu´ımica 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, 38023 Braunschweig, Germany
ReceiVed July 14, 1995X
The reactions of Na2dmit (dmit ) 2-thioxo-1,3-dithiole-4,5-dithiolate) with AuClL in 1:2 ratios lead to [Au2(dmit)L2]
[L ) PPh3 (1), PPh2Me (2), PPhMe2 (3), PMe3 (4), CH2PPh3 (5), CH2PPh2Me (6), CH2PPhMe2 (7)]. Complexes
1, 2, and 5 react further with equimolecular amounts of [AuL(tht)]ClO4 (tht ) tetrahydrothiophene), affording
trinuclear complexes [Au3(dmit)L3]ClO4 (8-10). When the reactions of Na2dmit with AuClL are carried out in
1:1 ratios and in the presence of NBu4Br, mononuclear tricoordinated gold(I) complexes NBu4[Au(dmit)L] [L )
PPh3 (11), PPh2Me (12), PMe3 (13)] are obtained. Other anionic derivatives such as (PPN)2[Au2(dmit)X2] [X )
C6F5 (14), Cl (15a), Br (15b)] can be obtained either by reaction of Na2dmit with Q[Au(C6F5)X] in 1:2 ratio or
by addition of (PPN)X to the recently reported [Au2(dmit)(AsPh3)]. Oxidative reactions of 11, 12, and 14 or 15b
with excess (TTF)3(BF4)2 afford (TTF)2[Au(dmit)2] (16), (TTF)[Au2(dmit)(C6F5)2] (17), and (TTF)3[Au2(dmit)-
Br2] (18), respectively. Reaction of complex 14 with TCNQ gives the anionic gold(III) complex [Au(dmit)(C6F5)2]-
(19). Electrical conductivities of these complexes at room temperature in compacted pellets are 2 × 10-3 (16),
7 × 10-5 (17), and 2 × 10-2 (18) S‚cm-1. Electrocrystallization of 1 and 11 affords [Au2(dmit)2(PPh3)] (20) and
the known NBu4[Au(dmit)2], respectively. X-ray structure determinations were performed for complexes 1, 11,
and 19b.
Introduction
nonplanar dmit-metal complexes have been studied.10-14
Furthermore many of the known dmit complexes are homoleptic;
Metal complexes of the dmit [2-thioxo-1,3-dithiole-4,5-
dithiolate (C3S52-)] ligand have received considerable attention
in the last two decades,1,2 because some of them were reported
to exhibit high conductivities. After the discovery in 1986 of
the first formally inorganic molecular superconductor3 (TTF)-
[Ni(dmit)2] (TTF ) tetrathiafulvalene), the research activity in
this area was increased, and several (cation)x[M(dmit)2] com-
pounds (cation ) TTF, NMe4)3-8 have been synthesized that
show superconducting properties, including the recently reported
(R-EDT-TTF)[Ni(dmit)2], which is superconducting at ambient
pressure.9
only a few dmit complexes containing other ligands have been
reported, including [Au2(dmit)(PPh3)2], [Au3(dmit)(PPh3)3]ClO4,
and [Au4(dmit)2(dppm)2] recently reported by us.15
This paper reports a synthetic study of heteroleptic gold(I)
derivatives [Au2(dmit)L2], [Au3(dmit)L3]ClO4, (NBu4)[Au-
(dmit)L], and (PPN)2[Au2(dmit)X2] and the products of reactions
with (TTF)3(BF4)2 and with TCNQ or electrochemical oxidation.
The molecular structures of [Au2(µ-dmit)(PPh3)2], (NBu4)[Au-
(dmit)(PPh3)], and (PPN)[Au(dmit)(C6F5)2] have been estab-
lished by single-crystal X-ray studies, showing that dmit can
act as a bridging or chelate ligand in gold chemistry.
Although nonplanar dmit-metal complexes are also expected
to behave as conductors on the basis of multidimensional
overlapping through the sulfur atoms of dmit ligands, few
Results and Discussion
The reaction of a methanolic solution of Na2dmit with
chlorogold(I) complexes [AuClL] (L ) phosphine or ylide) in
a molar ratio of 1:2 leads to dinuclear complexes where the
dmit ligand acts as a bridge between two gold centers (eq 1).
† Universidad de Zaragoza.
‡ Technische Universita¨t Braunschweig.
X Abstract published in AdVance ACS Abstracts, April 1, 1996.
(1) Cassoux, P.; Valade, L.; Kobayashi, H.; Kobayashi, A.; Clark. R. A.;
Underhill, A. E. Coord. Chem. ReV. 1991, 110, 115.
(2) Olk, R. M.; Olk, B.; Dietzsch, W.; Kirmse, R.; Hoyer, E. Coord. Chem.
ReV. 1992, 117, 99.
(3) Brossard, L.; Ribault, M.; Bousseau, M.; Valade, L.; Cassoux, P. C.
R. Acad. Sci. Paris, Ser. 2, 1986, 302, 205.
(4) Kobayashi, A.; Kim, H.; Sasaki, Y.; Kato, R.; Kobayashi, H.;
Moriyama, S.; Nishio, Y.; Kajita, K.; Sasaki, W. Chem. Lett. 1987,
1819.
(5) Brossard, L.; Hundequint, H.; Ribault, M.; Valade, L.; Legros, J. P.;
Cassoux, P. Synth. Met. 1988, 27, B157.
(1)
Complexes 1-7 are dark yellow (1, 3), red (2, 4), and garnet
(5-7) solids, air- and moisture-stable at room temperature. They
(6) Brossard, L.; Ribault, M.; Valade, L.; Cassoux, P. J. Phys. Fr. 1989,
50, 1521.
(7) Kobayashi, A.; Kobayashi, H.; Miyamoto, A.; Kato, R.; Clark, R. A.;
Underhill, A. E. Chem. Lett. 1991, 2163.
(10) Matsubayashi, G.; Akiba, K.; Tanaka, T. Inorg. Chem. 1988, 27, 4744.
(11) Akiba, K.; Matsubayashi, G.; Tanaka, T. Inorg. Chim. Acta 1989, 165,
245.
(8) Kobayashi, H.; Bun, K.; Naito, T.; Kato, R.; Kobayashi, A. Chem.
Lett. 1992, 1909.
(9) Tajima, H.; Inokuchi, M.; Kobayashi, A.; Ohta, T.; Kato, R.;
Kobayashi, H.; Kuroda, H. Chem. Lett. 1993, 1235.
(12) Broderick, W. E.; McGhee, E. M.; Cogfrey, M. R.; Hoffman, B. M.;
Ibers, J. A. Inorg. Chem. 1989, 28, 2904.
(13) Matsubayashi, G.; Yokozawa, A. J. Chem Soc., Chem. Commun. 1991,
68.
S0020-1669(95)00893-7 CCC: $12.00 © 1996 American Chemical Society

2996 Inorganic Chemistry, Vol. 35, No. 10, 1996
Cerrada et al.
Although the molecular structure shows two different Au-
PPh3 fragments, the 31P NMR spectrum consists of only one
resonance, because of fluxional behavior involving the two
Au-P units in solution, even at low temperature (-80 °C in
HDA).
Mass spectrometry data for complexes 1-7 indicate that a
further AuL unit could be incorporated into those complexes;
thus, the reaction of complexes 1, 2, and 5 with “[AuPPh3]+”
(generated in situ from AuClL and AgClO4) or with [AuL(tht)]-
ClO4 (tht ) tetrahydrothiophene) leads18b to trinuclear com-
plexes 8-10 (eq 2).
[Au2(µ-dmit)L2] + [AuL(tht)]ClO4 f
+ tht (2)
[Au3(µ3-dmit)L3]ClO4
L ) PPh3 (8), PPh2Me (9),
CH2PPh3 (10)
31P NMR spectra of these compounds at room temperature
each show a broad signal, which is resolved into two singlets
with a 2:1 intensity ratio at -80 °C. Complex 8 at low
temperature shows a broad singlet with a shoulder.
The structure of complex 8 has been reported previously by
us; it is very similar to that of complex 1, with one extra Au-
PPh3 fragment bonded through the thione group of the dmit
ligand.15 Presumably complexes 9 and 10 are further examples
of this µ3-dmit coordination mode.
When reaction 1 is carried out in a 1:1 molar ratio, a new
coordination mode of the dmit ligand is obtained: Na[Au-
(C3S5)L], where dmit chelates the gold center as part of a
trigonal coordination (eq 3). Addition of NBu4Br allows the
Figure 1. Molecule of complex 1 in the crystal (50% ellipsoids). H
atoms are omitted.
are nonconducting in acetone solution (≈5 × 10-4 M). Their
IR spectra show two bands at ca. 1050 (s) and 1034 (m) cm-1
that are assignable to υ(CdS)16 of the dmit ligand, a band at
1436 (s) cm-1 due to υ(CdC), and a band at ca. 580 (m) cm-1
17
assignable to υ(Au-Cylide
)
(5-7). Their 31P{1H} NMR
spectra each show a singlet, consistent with the presence of two
equivalent phosphorus atoms (see Table 1). The FAB+ mass
spectra for these complexes (NBA as matrix) show the [M+]
peak at m/z ) 1114 (55%, 1), 990 (15%, 2), 865 (100%, 3),
742 (100%, 4), 1142 (40%, 5), 1018 (13%, 6), and 894 (28%,
7). It is notable that peaks are present with higher m/z values
corresponding to [M + AuL]: 1573 (16%, 1), 1387 (20%, 2 ),
1015 (18%, 4), 1415 (45%, 5), and 1265 (16%, 6).
The structure of complex 1 has been established by X-ray
diffraction. The molecule is shown in Figure 1. Selected bond
lengths and angles are given in Table 3. As expected, the dmit
ligand bridges the two gold atoms through the sulfur atoms;
however, the mode of coordination is markedly nonsymmetric.
The linear coordination at Au(1) is typical of Au(I) complexes
[S(1)-Au(1)-P(1) ) 174.86(3)°], but the angle S(2)-Au(2)-
P(2) at Au(2) deviates considerably from linearity [159.32(4)°],
associated with a pseudotrigonal geometry including an extra
weak interaction Au(2)-S(1) ) 2.823(1) Å; Au(2) lies only
0.04 Å out of the plane of P(2), S(1), and S(2). There is a
intramolecular gold-gold contact of 3.0681(8) Å. The shorter
Au-S distances [S(1)-Au(1) ) 2.347(1), S(2)-Au(2) )
2.344(1) Å] are very similar to those found for other gold
dithiolate complexes [Au2(µ-i-MNT)(PPh3)2] [2.321(4), 2.313(2)
Å]18,19 and [Au2(µ-S2C6H4)(PPh3)2] [2.322(4) Å].18 Similar
distorted three-coordinate structures have been reported by
Fackler and Schmidbaur using other dithiolates.18-21
(3)
isolation of anionic complexes. The reaction functions only in
the case of L ) phosphine; a mixture of compounds results
when ylide is used instead, and complexes 5-7 can be detected
in the reaction mixture.
Complexes 11-13 are air- and moisture-stable red solids at
room temperature. They behave as 1:1 electrolytes in acetone
solution, and the IR spectra show bands characteristic of dmit
and phosphine ligands. Their 31P{1H} NMR spectra each show
a singlet from the single phosphine (see Table 1). The values
are displaced downfield with respect to the dinuclear com-
pounds, with the exception of that for L ) PMe3.
The trigonal coordination has been confirmed by X-ray
diffraction of a single crystal of complex 11. The structure
contains two independent formula units; one anion is shown in
Figure 2. Selected bond lengths and angles are given in Table
4. The gold atom displays regular three-coordination, with
similar Au-S distances involving the sulfur atoms of the
chelating dmit ligand [2.405(3), 2.476(3); 2.413(3), 2.483(3)
Å], with narrow S-Au-S angles of 89.6(1), 89.9(1)°. The
Au-S distances are slightly longer than those of complex 1,
presumably as a consequence of the more regular tricoordination.
However the Au-P bond lengths [2.235(2), 2.243(2) Å] are
slightly shorter than those in 1 [2.278(1), 2.257(1)Å].
Reaction 1 can be extended to ionic dinuclear compounds,
starting from Q[Au(C6F5)X] (Q ) NBu4, N(PPh3)2 (PPN); X
) Cl, Br), with which methanolic solutions of Na2dmit give
anionic complexes (eq 4).
(14) Frisch, E.; Polborn, K.; Robl, C.; Sunkel, K.; Bock, W. Z. Anorg.
Allg. Chem. 1993, 619, 2050.
(15) Cerrada, E.; Laguna, A.; Laguna, M.; Jones, P. G. J. Chem. Soc.,
Dalton Trans. 1994, 1325.
(16) Steimecke, G.; Sieler, H. J.; Kirmse R.; Hoyer, E. Phosphorus Sulfur
1979, 7, 49.
(17) Schmidbaur, H.; Franke, R. Inorg. Chim. Acta 1975, 13, 185; Chem.
Ber. 1975, 108, 1321; Angew. Chem., Int. Ed. Engl. 1973, 12, 416.
(18) (a) Da´vila, R. M.; Elduque, A.; Grant, T.; Staples, R. T.; Fackler, J.
P., Jr. Inorg. Chem. 1993, 32, 1749. (b) Gimeno, M. C.; Jones, P. G.;
Laguna, A.; Laguna, M.; Terroba, R. Inorg. Chem. 1994, 33, 3932.
(19) Ikhan, M. N.; Wang, S.; Heinrich, D. D.; Fackler, J. P., Jr. Acta
Crystallogr., C 1988, 44, 822.
(20) (a) Nakamoto, M.; Hiller, W.; Schmidbaur, H. Chem. Ber. 1993, 126,
605. (b) Nakamoto, M.; Koijman, H.; Paul, M.; Schmidbaur, H. Z.
Anorg. Allg. Chem. 1993, 619, 1341.
(21) Da´vila, R. M.; Staples, R. J.; Elduque, A.; Harlass, M. M.; Kyle, L.;
Fackler, J. P., Jr. Inorg. Chem. 1994, 33, 5940.

Heteroleptic dmit Complexes of Gold
Inorganic Chemistry, Vol. 35, No. 10, 1996 2997
Na2dmit + 2Q[Au(C6F5)X] f Q2[Au2(µ-dmit)(C6F5)2]
Q ) NBu4 (14a), PPN (14b)
(4)
These compounds can be isolated as dark pink (14a) or
orange-pink (14b) solids, air- and moisture-stable at room
temperature. They behave as 2:1 electrolytes in acetone
solution. Their IR spectra show the bands characteristic of dmit
and two bands at ca. 950 (s) and 790 (m) cm-1 due to C6F5
groups. The 19F NMR spectra show three groups of signals
with a pattern similar to those for other (pentafluorophenyl)-
gold(I) fragments.
Figure 2. Molecule of complex 11 in the crystal (50% ellipsoids). H
atoms are omitted.
When Q[AuX2] (X ) halogen) is used in reaction 1, a mixture
of complexes is obtained and the oxidation product, Q[Au-
(dmit)2], can be isolated. For this reason, we have used an
alternative procedure, starting from [Au2(dmit)(AsPh3)]n (re-
ported previously by us15 in the presence of 2 equiv of (PPN)X
(X ) Cl, Br); triphenylarsine is replaced by the halide (eq 5).
The electron spin resonance (ESR) results measured at 300
K can be summarized as follows: g| ) 2.0080, g ) 2.0037,
and half-width of 0.5 mT for 16; g ) 2.0083 and half-width of
1 mT for 17; and g ) 2.0077 and halfwidth of 2mT for 18.
The g values indicate that the resonance can be assigned to the
presence of the TTF•+ radical.
[Au2(dmit)(AsPh3)] + 2(PPN)X f
Conductivity measurements were carried out at ambient
pressures in the temperature range 295 -240 K using the two-
probe method in compacted pellets. Complexes 16 and 17
showed semiconducting behavior in the whole temperature range
with room-temperature values of 2 × 10-3 and 7 × 10-5
S‚cm-1, respectively, and activation energies of 0.06 and 0.59
eV. These values are similar to those of other reported gold
complexes28 but, in some cases, are lower that those reported
for some (NR4)x[M(dmit)2] complexes (M ) Ni, Pd, Pt).1,2
Complex 18 showed a conductivity value of 2 × 10-2 S.cm-1
at room temperature which increases in the temperature range
studied, being 3.3 × 10-2 at 240 K. Because these data are
measured on compresed pellets, we cannot conclude a metallic
behavior.
(PPN)2[Au2(µ-dmit)X2] + AsPh3 (5)
X ) Cl (15a), Br (15b)
These complexes are air- and moisture-stable pale brown
solids. They behave as 2:1 electrolytes in acetone solution, and
their IR spectra show bands at 326 (m) (15a) and 220 (m) (15b)
cm-1 assignable to υ(Au-X).
Oxidation Reactions. We performed various oxidation reac-
tions on the anionic derivatives, treating them with (TTF)3(BF4)2
(TTF ) tetrathiafulvalene) or TCNQ (7,7′,8,8′-tetracyanoquin-
odimethane), or on the neutral derivatives such as complex 1
by electrocrystallization procedures. Complexes 11, 12, 14, and
15 react with an excess of (TTF)3(BF4)2 in acetonitrile leading
to the precipitation of dark solids, insoluble in common organic
solvents, according to eqs 6-8.
The reaction of complex 14 with TCNQ in a 1:1 ratio leads
to the oxidation of one gold atom of the compound, giving a
gold(III) complex according to eq 9.
(TTF) [Au(dmit) ]
(NBu4)[Au(dmit)L] + (TTF)3(BF4)2 f
L ) PPh3, PPh2Me
2
2
16
(6)
Q [Au (µ-dmit)(C F ) ]
+ (TTF)3(BF4)2 f
2
2
6 5 2
Q ) NBu4, PPN
(9)
(TTF)[Au2(dmit)(C6F5)2]
(7)
(8)
17
Complexes 19a,b are air- and moisture-stable brown solids
at room temperature. They behave as 1:1 electrolytes in acetone
solution. The IR spectra show bands from the ligand [1443 (s)
cm-1 (υ(CdC)) and 1028 (m), 1056 (s) cm-1 (υ(CdS))] and
bands at 952 (m), 810 (m), and 780 (m) cm-1, corresponding
to the presence of two C6F5 groups. Their 19F NMR spectra
show three groups of signals characteristic of the presence of
two pentafluorophenyl groups in cis positions related by a
symmetry plane and with a free rotation around the ipso carbon
(see Experimental Section).
(PPN)2[Au2(µ-dmit)Br2] + (TTF)3(BF4)2 f
(TTF)3[Au2(dmit)Br2]
18
Because of the insolubility of complexes 16-18, their
stoichiometry can be given on the basis of only C, H, N, and
gold anayses (see Table 1 and Experimental Section). The
oxidation states of dmit and TTF cannot be accurately deter-
mined. The infrared spectra show absorptions (KBr pellets) at
ca. 1437 cm-1 for complexes 16 and 18, characteristic of
2- 22
(24) Bozio, R.; Girlando, A.; Pecile, D. Chem. Phys. Lett. 1977, 52, 503.
(25) Matsuzaki, S.; Moriyama, T.; Toyoda, K. Solid State Commun. 1980,
34, 857.
(26) Bozio, R.; Zanon, I.; Girlando, A.; Pecile, D. J. Chem. Phys. 1979,
71, 2282.
(27) (a) Jones, P. G.; Bembeneck, E. Z. Kristallogr. 1994, 209, 690. (b)
Uso´n, R.; Laguna, A.; Vicente, J.; Garcia, J.; Jones, P. G.; Sheldrick,
G. M. J. Chem. Soc., Dalton Trans. 1981, 655. (c) Uso´n, R.; Laguna,
A.; Laguna, M.; Castilla, M. L.; Jones, P. G.; Meyer-Ba¨se, K. J. Chem.
Soc. 1987, 336, 453.
(28) Matsubayashi, G.; Yokozawa, A. J. Chem. Soc., Dalton Trans. 1990,
3535.
C3S5
,
and at 1350 cm-1 in complex 17, which can be
- 23
assigned to C3S5
.
The Raman spectra of 16-18 show bands
at ca. 1440 cm-1, which might be attributed to the stretching
vibration of the central CdC bond of TTF, suggesting a partially
oxidized moiety.24-26 Complex 18 shows in addition an
absorption at 1413 cm-1 characterictic of TTF+ 25,26
.
(22) Matsubayashi, G.; Akiba, K.; Tanaka, T. Inorg. Chem. 1988, 27, 4744.
(23) Sakamoto, Y.; Matsubayashi, G.; Tanaka, T. Inorg. Chim. Acta 1986,
113, 137.

2998 Inorganic Chemistry, Vol. 35, No. 10, 1996
Cerrada et al.
hydrazine. Conductivities were measured in acetone with a Philips
PW 9509 apparatus, and mass spectra were recorded on a VG Autospec.
The ESR spectra were recorded at 300 K on a Bruker ESP 300 E
spectrometer. The microwave frequency was measured using a 5350
B microwave frequency counter from Hewlett-Packard, and the
magnetic field, with an ER 035 M NMR gaussmeter from Bruker.
Estimated errors in the g values are better than (0.0002.
The yields, elemental analyses, and 31P{1H} and some 1H NMR data
are listed in Table 1.
Safety 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.
Preparations. [Au2(µ-dmit)(L)2] [L ) PPh3 (1), PPh2Me (2),
PPhMe2 (3), PMe3 (4), CH2PPh3 (5), CH2PPh2Me (6), CH2PPhMe2
(7)]. Sodium metal (9 mg, 0.4 mmol) and 4,5-bis(benzoylthio)-1,3-
dithiole-2-thione (81 mg, 0.2 mmol) were dissolved under dinitrogen
atmosphere in methanol (20 mL) to give a dark red solution of
Na2[C3S5], to which was added AuCl(PPh3) (197 mg, 0.4 mmol),
AuCl(PPh2Me) (173 mg, 0.4 mmol), AuCl(PPhMe2) (148 mg, 0.4
mmol), AuCl(PMe3) (123 mg, 0.4 mmol), AuCl(CH2PPh3) (101 mg,
0.4 mmol), AuCl(CH2PPh2Me) (89 mg, 0.4 mmol) or AuCl(CH2-
PPhMe2) (80 mg, 0.4 mmol). Complexes 1-7 precipitated immediately
[dark yellow (1, 3), red (2, 4), garnet (5-7)], were collected by filtration,
washed with methanol, and dried in Vacuo. Yields (%): 91 (1), 80
(2), 75 (3), 77 (4), 85 (5), 87 (6), 90 (7). 1H NMR (in ppm): δ(Me)
1.96 (d, 9.7 Hz) (2), 1.72 (d, 12 Hz) (3), 1.58 (d, 10.7 Hz) (4), 2.3 (d,
11.7 Hz) (6), 2.03 (d, 12.6 Hz) (7); δ(-CH2-) 1.96 (d, 12.2 Hz) (5),
1.7 (d, 11.7 Hz) (6), 1.52 (d, 12.6 Hz) (7).
Figure 3. Formula unit of complex 19b in the crystal (50% ellipsoids).
H atoms are omitted.
The reaction with complexes 11-13 and 15 takes place in a
similar way, and Q(TCNQ) can be detected, but we were not
able to obtain the expected dmit derivatives in a pure form,
because Q(TCNQ) was always present in the crude products.
The crystal structure of complex 19b has been established
by X-ray analysis. The formula unit is shown in Figure 3.
Angles and distances are listed in Table 5. The anion shows
the gold center in a square-planar geometry (mean deviation of
five atoms 0.02 Å) typical of Au(III), with two C6F5 groups in
cis positions and a chelating dmit ligand. Au-S bond lengths
[2.322(2), 2.324(2) Å] are slightly shorter than those of
equivalent moieties in complex 8. Au-C distances involving
the Au-C6F5 units [2.061(6), 2.059(5) Å] are similar to those
in other gold(III) complexes [Au(C6F5)4]- [2.054(7)-2.058-
(8)Å]27a,b and [Au(C6F5)2{S2CN(CH2Ph)2}] [2.047(6), 2.049-
(6) Å].27c
When complex 1 is subjected to a constant current in an
H-tube (MeCN, NBu4[Au(C6F5)2], or NBu4ClO4, i ) 1.3 µA),
black microcrystals form, for which elemental analysis indicates
the formula [Au2(dmit)2(PPh3)] (20). The insolubility of the
crystals in all common solvents precludes the recording of NMR
data, and their poor quality makes X-ray analysis impossible.
However, complex 11 under similar conditions gives the known
gold(III) complex NBu4[Au(dmit)2].28 The electrical conductiv-
ity of complex 20 at room temperature in compacted pellets is
1.3 × 10-5 S.cm-1 and shows the behavior of a semiconductor
with an activation energy of 0.56 eV. Complex 20 does not
exhibit an electron spin resonance signal, showing that the dmit
ligand is not oxidized in this complex.
[Au3(µ3-dmit)(L)3]ClO4 [L ) PPh3 (8), PPh2Me (9), CH2PPh3
(10)]. To a dichloromethane solution of [AuCl(PPh3)] (49 mg, 0.1
mmol), [AuCl(PPh2Me)] (43 mg, 0.1 mmol), or [AuCl(CH2PPh3)] (50
mg, 0.1 mmol) was added AgClO4 (20 mg, 0.1 mmol). After 1 h of
stirring, the suspension was filtered through 1 cm of Celite, and [Au2-
(µ-dmit)(PPh3)2] (111 mg, 0.1 mmol), [Au2(µ-dmit)(PPh2Me)2] (99 mg,
0.1 mmol), or [Au2(µ-dmit)(CH2PPh3)2] (114 mg, 0.1 mmol) was added
to the resulting solution. After 3 h of stirring, the solutions were
concentrated by evaporation, and the addition of diethyl ether led to
precipitation of dark garnet solids that were filtered off and dried in
Vacuo. Yields (%): 76 (8), 63 (9), 88 (10). 1H NMR (in ppm): δ(Me)
1.96 (d, 9.8 Hz) (9); δ(-CH2-) 1.9 (s, br) (10).
(NBu4)[Au(dmit)L] [L ) PPh3 (11), PPh2Me (12), PMe3 (13)].
4,5-Bis(benzoylthio)-1,3-dithiole-2-thione (81 mg, 0.2 mmol) was
dissolved under dinitrogen atmosphere in a methanol (20 mL) solution
containing sodium metal (9 mg, 0.4 mmol), affording Na2[C3S5]. A
dichloromethane (5 mL) solution of AuCl(PPh3) (98 mg, 0.2 mmol),
AuCl(PPh2Me) (86 mg, 0.2 mmol), or AuCl(PPMe3) (62 mg, 0.2 mmol)
was added followed by a dichloromethane (5 mL) solution of (NBu4)-
Br (64 mg, 0.2 mmol) with stirring. The solutions turned red. After
12 h of stirring the solutions were evaporated to dryness, and acetone
(15 mL) was added, affording a white solid (NaCl), which was filtered
off. The solutions were concentrated to 5 mL. Addition of diethyl
ether precipitated red solids (11-13). Yields (%): 87 (11), 76 (12),
50 (13). 1HNMR (in ppm): δ(Me) 2.1 (d, 8.8 Hz) (12), 1.55 (d, 10.1
Hz) (13).
Experimental Section
Materials. 4,5-Bis(benzoylthio)-1,3-dithiole-2-thione,16,29 [AuCl-
(PR3)],30 [AuCl(CH2PR3)],31 Q[Au(C6F5)X],30 [Au2(C3S5)(AsPh3)],15 and
32
Q2[Au2(µ-dmit)(C6F5)2] [Q ) NBu4 (14a), N(PPh3)2 (PPN) (14b)].
Sodium metal (9 mg, 0.4 mmol) and 4,5-bis(benzoylthio)-1,3-dithiole-
2-thione (81 mg, 0.2 mmol) were dissolved under dinitrogen atmosphere
in methanol (20 mL) to give a dark red solution, to which was added
(NBu4)[Au(C6F5)Br] (274 mg, 0.4 mmol) or (PPN)[Au(C6F5)Cl] (375
mg, 0.4 mmol). Immediately pink complexes (14a,b) precipitated, were
collected by filtration, washed with methanol, and dried in Vacuo. Yields
(%): 70 (14a), 80 (14b). 19F NMR (in ppm): δ(14a) -115.6 (m, Fo),
-163.4 (t, Fp), -164.6(m, Fm); δ(14b) -115.0 (m, Fo), -163.4 (t, Fp),
-164.6 (m, Fm).
(TTF)3(BF4)2 were obtained according to the literature procedures.
General Data. Infrared spectra were recorded on a Perkin-Elmer
559 or 883 spectrophotometer over the range 4000-200 cm-1 (Nujol
1
mulls between polyethylene sheets), and H and 31P NMR spectra, on
a Varian UNITY 300 in CDCl3 solutions; chemical shifts are quoted
relative to SiMe4 (1H) and H3PO4 (external 31P). The C, H, N, and S
analyses were performed with a Perkin-Elmer 2400 microanalyzer; Au
was determined by ashing the samples with an aqueous solution of
(29) Valade, L.; Legros, J. P.; Bousseau, M.; Cassoux, P.; Barbauskas, M.;
Interrante, L. V. J. Chem. Soc., Dalton Trans. 1985, 783.
(30) Uso´n, R.; Laguna, A. Organomet. Synth. 1985, 3, 325.
(31) Uso´n, R.; Laguna, A.; Laguna, M.; Uso´n, A.; Gimeno, M. C. Inorg.
Chim. Acta 1986, 114, 91.
(PPN)2[Au2(µ-dmit)(X)2] [X ) Cl (15a), Br (15b)]. To an acetone
(20 mL) suspension of [Au2(C3S5)(AsPh3)] (89 mg, 0.1 mmol) was
added (PPN)Br (123 mg, 0.2 mmol) or (PPN)Cl (114 mg, 0.2 mmol).
The solution turned orange. After being stirred for 12 h, the solution
(32) Wuld, F. J. Am. Chem. Soc. 1975, 79, 1962.

Heteroleptic dmit Complexes of Gold
Inorganic Chemistry, Vol. 35, No. 10, 1996 2999
Table 1. Analytical and Spectroscopic Data
anal. (%)a
b
no.
complex
C
H
N
S
ΛM
δ(31P NMRd)
1
2
3
4
5
6
7
8
[Au2(µ-dmit)(PPh3)2]
42.15 (42.0)
35.15 (35.15)
26.05 (26.35)
15.0 (14.6)
42.6 (43.1)
36.8 (36.55)
27.8 (28.2)
41.1 (40.9)
34.05 (33.9)
42.0 (42.0)
50.0 (49.5)
46.0 (46.0)
36.45 (37.1)
40.05 (40.05)
51.95 (52.2)
49.65 (49.3)
51.7 (51.8)
21.45 (21.65)
22.35 (22.35)
18.65 (18.5)
38.7 (38.4)
48.75 (48.4)
27.5 (27.5)
2.55 (2.7)
3.45 (3.3)
2.45 (2.55)
2.4 (2.45)
2.9 (3.0)
2.85 (2.95)
2.5 (2.9)
14.05 (14.4)
15.7 (16.2)
18.09 (18.5)
21.6 (21.6)
14.0 (14.0)
15.4 (15.7)
16.9 (17.9)
9.8 (9.6)
10.2 (10.7)
9.2 (9.3)
17.65 (17.85)
19.0 (19.2)
21.15 (22.5)
11.75 (11.4)
7.69 (8.0)
8
2
5
2
9
7
9
113
124
97
88
100
101
171
204
233
205
c
c
c
120
121
c
36.5 (s)
19.4 (s)
7.4 (s)
-4.4 (s)
31.0 (s)
[Au2(µ-dmit)(PPh2Me)2]
[Au2(µ-dmit)(PPhMe2)2]
[Au2(µ-dmit)(PMe3)2]
[Au2(µ-dmit)(CH2PPh3)2]
[Au2(µ-dmit)(CH2PPh2Me)2]
[Au2(µ-dmit)(CH2PPhMe2)2]
[Au3(µ3-dmit)(PPh3)3]ClO4
[Au3(µ3-dmit)(PPh2Me)3]ClO4
[Au3(µ3-dmit)(CH2PPh3)3]ClO4
(NBu4)[Au(dmit)(PPh3)]
(NBu4)[Au(dmit)(PPh2Me)]
(NBu4)[Au(dmit)(PMe3)]
(NBu4)2[Au2(µ-dmit)(C6F5)2]
(PPN)2[Au2(µ-dmit)(C6F5)2]
(PPN)2[Au2(µ-dmit)Br2]
(PPN)2[Au2(µ-dmit)Cl2]
(TTF)2[Au(dmit)2]
27.7 (s)
26.5 (s)
2.5 (2.7)
35.7 (s,br)e
19.2 (s,br)e
30.7 (s,br)e
42.3 (s)
9
2.3 (2.65)
3.15 (3.0)
5.8 (5.7)
5.65 (5.9)
6.0 (6.4)
5.15 (5.15)
2.9 (3.0)
3.4 (3.3)
3.6 (3.5)
0.9 (0.8)
0.55 (0.35)
0.85 (0.9)
4.3 (4.05)
2.15 (2.4)
1.35 (1.45)
10
11
12
13
14a
14b
15a
15b
16
17
18
19a
19b
20
1.8 (1.55)
1.7 (1.7)
1.8 (2.0)
1.85 (2.0)
1.45 (1.4)
1.5 (1.55)
1.7 (1.6)
23.3 (s)
-6.5 (s)
7.8 (8.8)
10.1 (9.25)
56.65 (57.8)
26.8 (25.55)
40.5 (40.0)
19.0 (19.9)
15.7 (14.7)
30.2 (30.55)
(TTF)[Au2(dmit)(C6F5)2]
(TTF)3[Au2(dmit)Br2]
(NBu4)[Au(dmit)(C6F5)2]
(PPN)[Au(dmit)(C6F5)2]
[Au2(dmit)2(PPh3)]
1.95 (1.45)
1.35 (1.1)
a Calculated values are given in parentheses. b In acetone; values in Ω-1 cm2 mol-1
31.3, 31.5 (s, -80 °C). 9: 18.3, 20.0 (s, -80 °C). 10: 30.9, 31.4 (s, -60 °C).
.
c Low solubility. d δ in ppm. e At room temperature. 8:
Table 2. Crystallographic Data for Compounds 1, 11, and 19b
11 19b
C39H30Au2P2S5 C37H51AuNPS5 C51H30AuF10NP2S5
Table 3. Selected Bond Lengths (Å) and Angles (deg) for
Compound 1
1
Au(1)-P(1)
Au(1)-S(1)
Au(1)-Au(2)
Au(2)-P(2)
Au(2)-S(2)
Au(2)-S(1)
S(1)-C(1)
S(2)-C(2)
S(3)-C(3)
S(3)-C(1)
2.2779(11)
2.3474(11)
3.0681(8)
2.2569(12)
2.3435(12)
2.8226(14)
1.749(4)
1.740(4)
1.725(5)
1.745(4)
S(4)-C(3)
S(4)-C(2)
S(5)-C(3)
C(1)-C(2)
P(1)-C(11)
P(1)-C(31)
P(1)-C(21)
P(2)-C(51)
P(2)-C(61)
P(2)-C(41)
1.732(4)
1.756(4)
1.650(4)
1.362(5)
1.809(5)
1.824(4)
1.825(4)
1.818(4)
1.820(5)
1.820(5)
formula
Mr
1114.80
898.02
1265.97
crystal habit
yellow prism
red-brown
prism
orange prism
crystal size
(mm)
0.5 × 0.3 × 0.2 0.4 × 0.3 × 0.2 0.4 × 0.35 × 0.3
temp (°C)
crystal system
space group
a (Å)
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
-100
-95
-95
triclinic
P1h
monoclinic
Cc
monoclinic
P21/c
10.191(2)
12.550(3)
15.038(4)
85.36(2)
75.73(3)
89.88(2)
1857.5
2
1.993
8.3
0.63-0.99
1064
17.134(4)
30.080(5)
17.048(4)
90
115.76(2)
90
7913
8
1.508
4.0
12.911(3)
34.194(7)
11.657(3)
90
110.71(2)
90
4814
4
1.747
3.4
P(1)-Au(1)-S(1)
174.86(3)
P(1)-Au(1)-Au(2) 113.75(4)
C(1)-C(2)-S(2)
C(1)-C(2)-S(4)
S(2)-C(2)-S(4)
S(5)-C(3)-S(3)
S(5)-C(3)-S(4)
S(3)-C(3)-S(4)
C(11)-P(1)-C(31) 106.2(2)
C(11)-P(1)-C(21) 108.0(2)
C(31)-P(1)-C(21) 104.7(2)
129.4(3)
114.6(3)
116.0(2)
123.7(3)
124.6(3)
111.8(2)
S(1)-Au(1)-Au(2)
P(2)-Au(2)-S(2)
P(2)-Au(2)-S(1)
S(2)-Au(2)-S(1)
61.12(4)
159.32(4)
115.05(4)
85.52(4)
Z
Dx (Mg m-3
)
P(2)-Au(2)-Au(1) 103.10(3)
µ (mm-1
transm
)
S(2)-Au(2)-Au(1)
S(1)-Au(2)-Au(1)
C(1)-S(1)-Au(1)
C(1)-S(1)-Au(2)
Au(1)-S(1)-Au(2)
C(2)-S(2)-Au(2)
C(3)-S(3)-C(1)
C(3)-S(4)-C(2)
C(2)-C(1)-S(3)
C(2)-C(1)-S(1)
S(3)-C(1)-S(1)
92.54(3)
46.74(2)
0.72-0.89
3632
0.74-0.86
2488
F(000)
102.39(13) C(11)-P(1)-Au(1) 112.55(12)
2θmax (deg)
no. of reflns
measd
55
50
50
93.36(13) C(31)-P(1)-Au(1) 114.47(12)
72.14(3)
C(21)-P(1)-Au(1) 110.35(12)
11 824
8578
0.037
0.063
12 656
12 218
0.021
9221
8507
0.030
0.086
104.15(14) C(51)-P(2)-C(61) 104.3(2)
98.6(2)
98.8(2)
116.2(3)
127.3(3)
116.5(2)
indep
Rint
C(51)-P(2)-C(41) 105.7(2)
C(61)-P(2)-C(41) 103.6(2)
C(51)-P(2)-Au(2) 112.10(13)
C(61)-P(2)-Au(2) 115.87(13)
C(41)-P(2)-Au(2) 114.23(14)
R
w (F 2,
0.103
all reflns)a
R(F, >4σ(F))b
no. of params
0.025
434
0.041
431
0.034
631
no. of restraints 354
138
1.01
<0.001
1.10
541
1.02
<0.001
1.48
solution of 11 (0.089 g, 0.1 mmol) or 12 (0.083 g, 0.1 mmol) to yield
immediately a dark brown solid, which was filtered off and washed
with acetonitrile. Anal. Calcd for C18H8S18Au: Au, 19.7. Found: Au,
18.8.
Sc
1.04
max ∆/σ
<0.001
1.32
max ∆F (e Å-3
)
a Rw(F2) ) [∑{w(Fo2 - Fc2)2}/∑{w(Fo )2}]0.5; w-1 ) σ2(Fo ) + (aP)2
+ bP, where P ) [Fo2 + 2Fc2]/3 and a and b are constants adjusted by
the program. b R(F) ) ∑||Fo| - |Fc||/∑|Fo|. c S ) [∑{w(Fo2 - Fc2)2}/
(n - p)]0.5, where n is the number of data and p the number of
parameters.
2
2
(TTF)[Au2(dmit)(C6F5)2] (17). An acetonitrile (20 mL) solution
of (TTF)3(BF4)2 (0.05 g, 0.065 mmol) was added to an acetonitrile (10
mL) solution of 14b (0.1 g, 0.05 mmol) to yield immediately a dark
garnet solid, which was filtered off and washed with acetonitrile. Anal.
Calcd for C21H4S14F10Au2: Au, 30.5. Found: Au, 29.6.
(TTF)3[Au2(dmit)Br2] (18). An acetonitrile (20 mL) solution of
(TTF)3(BF4)2 (0.078 g, 0.1 mmol) was added to an acetonitrile (10 mL)
solution of 15a (0.146 g, 0.08 mmol) to yield immediately a dark red
solid, which was filtered off and washed with acetonitrile. Anal. Calcd
for C21H12S17Br2Au2: Au, 28.9. Found: Au, 27.8.
was concentrated to 5 mL; addition of diethyl ether (15 mL) led to the
precipitation of brown solids (15a,b), which were filtered off and
washed with diethyl ether. Yields (%): 50 (15a), 52 (15b).
(TTF)2[Au(dmit)2] (16). An acetonitrile (20 mL) solution of (TTF)3-
(BF4)2 (0.102 g, 0.13 mmol) was added to an acetonitrile (10 mL)

3000 Inorganic Chemistry, Vol. 35, No. 10, 1996
Cerrada et al.
Table 5. Selected Bond Lengths (Å) and Angles (deg) for
Table 4. Selected Bond Lengths (Å) and Angles (deg) for
Compound 11
Compound 19b
Au(1)-P(1)
Au(1)-S(2)
Au(1)-S(1)
P(1)-C(11)
P(1)-C(21)
P(1)-C(31)
S(1)-C(1)
S(2)-C(2)
S(3)-C(3)
S(3)-C(1)
S(4)-C(3)
S(4)-C(2)
S(5)-C(3)
C(1)-C(2)
2.235(2)
2.405(3)
2.476(3)
1.809(10)
1.846(10)
1.849(9)
1.715(10)
1.748(10)
1.727(10)
1.759(10)
1.749(10)
1.761(9)
1.632(9)
1.352(13)
Au(1′)-P(1′)
Au(1′)-S(2′)
Au(1′)-S(1′)
P(1′)-C(11′)
P(1′)-C(31′)
P(1′)-C(21′)
S(1′)-C(1′)
S(2′)-C(2′)
S(3′)-C(3′)
S(3′)-C(1′)
S(4′)-C(3′)
S(4′)-C(2′)
S(5′)-C(3′)
C(1′)-C(2′)
2.243(2)
2.413(3)
2.483(3)
1.796(10)
1.816(10)
1.821(10)
1.750(9)
1.712(9)
1.722(10)
1.738(9)
1.700(10)
1.761(8)
1.670(10)
1.370(12)
Au-C(21)
Au-C(11)
Au-S(1)
2.059(5)
2.061(6)
2.3215(14)
2.324(2)
1.747(5)
1.752(5)
S(3)-C(3)
S(3)-C(1)
S(4)-C(3)
S(4)-C(2)
S(5)-C(3)
C(1)-C(2)
1.731(6)
1.750(5)
1.739(6)
1.739(5)
1.647(6)
1.340(7)
Au-S(2)
S(1)-C(1)
S(2)-C(2)
C(21)-Au-C(11)
C(21)-Au-S(1)
C(11)-Au-S(1)
C(21)-Au-S(2)
C(11)-Au-S(2)
S(1)-Au-S(2)
C(1)-S(1)-Au
C(2)-S(2)-Au
C(3)-S(3)-C(1)
C(3)-S(4)-C(2)
C(2)-C(1)-S(3)
90.4(2)
C(2)-C(1)-S(1)
125.1(4)
89.19(13) S(3)-C(1)-S(1)
178.9(2)
178.61(11) C(1)-C(2)-S(2)
88.79(14) S(4)-C(2)-S(2)
91.68(5)
99.4(2)
99.5(2)
97.8(3)
98.4(3)
116.4(4)
118.4(3)
115.7(4)
124.3(4)
120.0(3)
124.0(3)
124.3(3)
111.7(3)
C(1)-C(2)-S(4)
S(5)-C(3)-S(3)
S(5)-C(3)-S(4)
S(3)-C(3)-S(4)
C(16)-C(11)-C(12) 116.4(5)
C(22)-C(21)-C(26) 115.5(5)
P(1)-Au(1)-S(2)
P(1)-Au(1)-S(1)
S(2)-Au(1)-S(1)
142.78(9) P(1′)-Au(1′)-S(2′)
127.20(9) P(1′)-Au(1′)-S(1′)
89.57(8) S(2′)-Au(1′)-S(1′)
138.33(9)
131.60(9)
89.91(9)
C(11)-P(1)-C(21) 104.6(4)
C(11)-P(1)-C(31) 101.3(4)
C(21)-P(1)-C(31) 105.0(4)
C(11)-P(1)-Au(1) 117.3(3)
C(21)-P(1)-Au(1) 109.9(3)
C(31)-P(1)-Au(1) 117.4(3)
C(11′)-P(1′)-C(31′) 103.9(4)
C(11′)-P(1′)-C(21′) 105.3(4)
C(31′)-P(1′)-C(21′) 101.3(4)
C(11′)-P(1′)-Au(1′) 115.2(3)
C(31′)-P(1′)-Au(1′) 113.2(3)
C(21′)-P(1′)-Au(1′) 116.2(3)
platinum wires as anode and cathode. Black microcrystals of complex
20 formed on the anode and were collected and dried in Vacuo.
Crystal Structure Analyses. Crystal data are presented in Table
2. Data collection: Data were collected with Mo KR radiation on a
Siemens R3 diffractometer equipped with an LT-2 low-temperature
device; scan type ω. Cell constants were refined from setting angles
of ca. 50 reflections in the 2θ range 20-23°. Absorption corrections
based on ψ scans were applied. Structure solution: heavy-atom
method. Structure refinement: anisotropic refinement on F2,33 H atoms
as rigid methyls or with a riding model, weighting scheme w-1 ) σ2(F2)
C(1)-S(1)-Au(1)
C(2)-S(2)-Au(1)
C(3)-S(3)-C(1)
C(3)-S(4)-C(2)
C(2)-C(1)-S(1)
C(2)-C(1)-S(3)
S(1)-C(1)-S(3)
C(1)-C(2)-S(2)
C(1)-C(2)-S(4)
S(2)-C(2)-S(4)
S(5)-C(3)-S(3)
S(5)-C(3)-S(4)
S(3)-C(3)-S(4)
97.8(4)
98.4(3)
C(1′)-S(1′)-Au(1′)
C(2′)-S(2′)-Au(1′)
C(3′)-S(3′)-C(1′)
C(3′)-S(4′)-C(2′)
C(2′)-C(1′)-S(3′)
C(2′)-C(1′)-S(1′)
S(3′)-C(1′)-S(1′)
C(1′)-C(2′)-S(2′)
C(1′)-C(2′)-S(4′)
S(2′)-C(2′)-S(4′)
S(5′)-C(3′)-S(4′)
S(5′)-C(3′)-S(3′)
S(4′)-C(3′)-S(3′)
97.1(3)
98.4(3)
100.4(5)
99.3(5)
98.2(5)
99.7(5)
126.7(9)
114.5(8)
118.6(6)
127.3(8)
115.6(8)
117.0(6)
126.2(6)
123.9(6)
109.8(5)
116.7(7)
125.3(7)
117.9(5)
128.9(7)
113.0(7)
118.0(6)
123.1(6)
124.6(6)
112.3(5)
2
+ (aP)2 + bP, where 3P ) (2Fc2 + Fo ), and a and b are constants
optimized by the program. A variety of restraints were applied to light-
atom displacement parameters (DELU) and aromatic rings (FLAT,
SAME).
Special features of refinement: For 11, the absolute structure was
determined by an x refinement34 and the origin was fixed in terms of
a weighted sum of coordinates;35 C and N atoms were refined
isotropically.
Q[Au(dmit)(C6F5)2] [Q ) NBu4 (19a), N(PPh3)2 (PPN) (19b)]. To
a dichloromethane (15 mL) solution of complex 14 [(NBu4)2[Au2(µ-
C3S5)(C6F5)2] (84 mg, 0.06 mmol) or (PPN)2[Au2(µ-C3S5)(C6F5)2] (120
mg, 0.06 mmol)] was added a dichloromethane solution of TCNQ (12
mg, 0.06 mmol). The solutions turned dark green. After 3 h of stirring,
the solutions were concentrated to 1 mL, and the addition of diethyl
ether (20 mL) precipitated a green solid [Q(TCNQ)], which was filtered
off and washed with diethyl ether. The remaining solutions were
concentrated to 5 mL, whereupon addition of hexane (15 mL)
precipitated brown solids (19a,b). Yields (%): 55 (19a), 80 (19b).
19F NMR: δ(19a) -115.6 (m, Fo), -161.6 (t, Fp), -163.4 (m, Fm);
δ(19b) -115.4 (m, Fo), -163.2 (t, Fp), -164.6 (m, Fm).
[Au2(dmit)2(PPh3)] (20) by Electrolysis. An acetonitrile (10 mL)
solution containing complex 1 (0.044 g, 0.04 mmol) and (NBu4)[Au-
(C6F5)2] (0.077 g, 0.1 mmol) or (NBu4)ClO4 (0.068 g, 0.1 mmol) was
subjected to a controlled-current (1.3 µΑ) electrolysis under a nitrogen
atmosphere for 15 d at room temperature in an H-type glass cell with
Final atomic coordinates are given in the Supporting Information,
and selected bond lengths and angles are given in Tables 3-5.
Acknowledgment. We thank the Direction General de
Investigacio´n Cient´ıfica y Te´cnica (PB92-1078) and the Fonds
der Chemischen Industrie for finnancial support.
Supporting Information Available: Tables of crystal data, data
collection and solution and refinement parameters, all atomic coordi-
nates, bond distances and angles, and thermal parameters (20 pages).
Ordering information is given on any current masthead page.
IC950893+
(33) Sheldrick, G. M. SHELXL-93, a program for refining crystal structures.
University of Go¨ttingen, 1993.
(34) Flack, H. D. Acta Crystallogr. 1983, A39, 876.
(35) Flack, H. D.; Schwarzenbach, D. Acta Crystallogr. 1988, A44, 499.