Structural diversity in gold(I) complexes of 4-sulfanylbenzoic acid

Article abstract of DOI:10.1039/b100113m

Treatment of the gold(I) halide species AuLCl (where L = PMe₃, PEt₃, PPh₃, PPh₂(C₅H₄N-2) or SPPh₃) and (AuCl)2(P-P) (where P-P = 1,4-bis(diphenylphosphino)butane or 1,1′-bis(diphenylphosphino)ferrocene) with 4-sulfanylbenzoic acid (1 or 2 equivalents as required) in the presence of sodium methoxide provided the corresponding phosphine gold(I) thiolate complexes AuL(4-SC₆H₄CO₂H) and [Au(4-SC₆H₄CO₂H)]₂(P-P), respectively. Addition of two equivalents of the acid (in the presence of NaOMe) to [N(PPh₃)₂][AuCl₂] yielded the dithiolate species [(N(PPh)₃)₂][Au(4-SC₆ H₄CO₂H)₂]. A polyaurated product [(Ph₃PAu)₂(4-SC₆H₄ CO₂H)]BF₄ was obtained on treating the acid with the oxonium complex [(Ph₃PAu)₃O]BF₄. The species AuL(4-SC₆H₄CO₂H) (L = PEt₃, PPh₃ or PPh₂C₅H₄N-2)) have been investigated crystallographically and reveal diverse structures incorporating aurophilic contacts, Au···S interactions and hydrogen bonding.

Full text of DOI:10.1039/b100113m

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Structural diversity in gold(I) complexes of 4-sulfanylbenzoic acid
James D. E. T. Wilton-Ely, Annette Schier, Norbert W. Mitzel and Hubert Schmidbaur*
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4,
D-85747 Garching, Germany
Received 2nd January 2001, Accepted 7th February 2001
First published as an Advance Article on the web 14th March 2001
Treatment of the gold() halide species AuLCl (where L = PMe3, PEt3, PPh3, PPh2(C5H4N-2) or SPPh3) and
(AuCl)2(P–P) (where P–P = 1,4-bis(diphenylphosphino)butane or 1,1Ј-bis(diphenylphosphino)ferrocene)
with 4-sulfanylbenzoic acid (1 or 2 equivalents as required) in the presence of sodium methoxide provided the
corresponding phosphine gold() thiolate complexes AuL(4-SC6H4CO2H) and [Au(4-SC6H4CO2H)]2(P–P),
respectively. Addition of two equivalents of the acid (in the presence of NaOMe) to [N(PPh3)2][AuCl2] yielded
the dithiolate species [N(PPh3)2][Au(4-SC6H4CO2H)2]. A polyaurated product [(Ph3PAu)2(4-SC6H4CO2H)]BF4
was obtained on treating the acid with the oxonium complex [(Ph3PAu)3O]BF4. The species AuL(4-SC6H4CO2H)
(L = PEt3, PPh3 or PPh2(C5H4N-2)) have been investigated crystallographically and reveal diverse structures
incorporating aurophilic contacts, Au ؒ ؒ ؒ S interactions and hydrogen bonding.
Introduction
Preparative studies
Gold thiolates are an extremely important class of gold com-
pounds. Complexes of the type Au(SR) or AuL(SR) (R = alkyl,
aryl, etc.; L = neutral donor ligand) are contained in most
“liquid golds” for the glass and ceramics industry, in gold
pastes used in the electrical industry and microelectronics, and
in gold drugs for chemotherapy.1 Gold thiolate functions are the
key connectivities between the surface of bulk gold and the
substrate films in self-assembly monolayer (SAM) nano-
technology.2 The high affinity of gold for the heavy chalcogen
elements (sulfur, selenium and tellurium) allows the synthesis
of many Au/S (Se,Te) preparations from gold salts and thioles
or thiolates, etc.,3 although most of these compounds are
thermodynamically unstable relative to gold metal and organic
disulfides.
(Phosphine)gold() complexes of 4-sulfanylbenzoic acid are
easily obtained from reactions of this acid with coordination
compounds of the type Au(R3P)Cl in methanol with an equiv-
alent amount of sodium methanolate. Four different tertiary
monophosphines were employed with R = Me (1), Et (2) or Ph
(3), and R3 = Ph2(C5H4N-2) (4) (Scheme 1). Two examples of
Many gold() thiolates (AuSR) and gold() thiolate complexes
AuL(SR) are known to aggregate either via intermolecular
aurophilic contacts (i.e. Au ؒ ؒ ؒ Au closed-shell interactions) or
intermolecular gold–sulfur coordination (Au ؒ ؒ ؒ S) depending
on the electronic or steric nature of the substituents. These
interactions lead to interesting supramolecular structures often
associated with intriguing photophysical properties. Theor-
etical work has predicted that Au ؒ ؒ ؒ Au contacts should be
particularly strong with sulfide or thiolate substituents,4 but
structural data do not always follow this pattern because
Au ؒ ؒ ؒ S contacts are also able to compete efficiently and a
delicate balance between the two types of interactions often
leads to unexpected results.5
Scheme 1
complexes bearing bisphosphines, [Au(4-SC6H4CO2H)]2(dppb)
5 [dppb = 1,4-bis(diphenylphosphino)butane] and [Au(4-SC6-
H4CO2H)]2(dppf) 6 [dppf = 1,1Ј-bis(diphenylphosphino)ferro-
cene], were prepared in a similar manner using two equivalents
of the acid and NaOMe from (AuCl)2(dppb) and (AuCl)2-
(dppf), respectively (Scheme 2). Two examples in which gold
is bound solely to sulfur were also investigated. In a similar
manner to the examples reported by Nakamoto and co-
workers,12 the compound [N(PPh3)2][Au(4-SC6H4CO2H)2] 7 was
obtained from the reaction of [N(PPh3)2][AuCl2] with 2 equiv-
alents of 4-sulfanylbenzoic acid in the presence of sodium
In the design of a structural pattern, crystal engineering,
other weak forces can be combined with Au ؒ ؒ ؒ Au/Au ؒ ؒ ؒ S
interactions, and recent attempts to incorporate hydrogen
bonding have been particularly successful.6,7 Ligands which
offer both thiolate and carboxylate functions were shown to be
instrumental in the construction of multidimensional arrays of
gold() complexes.8 Other systems probed successfully in this
context were those based on hydroxyphosphine/phosphinate,9
imidazole/imidazolate10 and phosphinophenol/phosphino-
phenolate11 complexes.
methoxide. The species Au(Ph P᎐S)Cl was also found to react
᎐
3
with the same acid in the presence of NaOMe to yield Au(Ph3-
P᎐S)(4-SC H CO H) 8. A polyaurated product [(Ph PAu) -
(4-SC6H4CO2H)]BF4 9 was obtained on treatment of the acid
with the oxonium salt [(Ph3PAu)3O]BF4.
All products were isolated in good yields as colourless or pale
yellow (in the case of 6) crystalline solids which were character-
ised by NMR spectroscopy (1H, 31P) and FAB mass spectro-
metry (where possible) and gave satisfactory elemental analyses
(see Experimental). The compounds 1–4 and 9 are soluble in
both dichloromethane and chloroform, and 5–8 dissolve in
(d6) dimethyl sulfoxide. The NMR spectra of these solutions
᎐
6
4
2
3
2
Our initial studies with 2-sulfanylbenzoic acid7 have now
been extended to include gold() 4-sulfanylbenzoic acid com-
plexes, in which a different geometrical orientation of the
substituents induces entirely different connectivity patterns.
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J. Chem. Soc., Dalton Trans., 2001, 1058–1062
This journal is © The Royal Society of Chemistry 2001
DOI: 10.1039/b100113m

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Scheme 2 (i) (dppb)(AuCl)2, NaOMe; (ii) (dppf )(AuCl)2, NaOMe; (iii) [PPN][AuCl2], NaOMe [PPN = N(PPh3)2ϩ]; (iv) (Ph3P᎐S)AuCl, NaOMe;
᎐
(v) [(Ph3PAu)3O]BF4, NaBF4.
show singlet signals for 31P-{1H} and the expected sets of
resonances in the 1H spectra.
The FAB mass spectra of complexes 1–4 showed the molec-
ular ions [M]ϩ preceded by the cation [M ϩ PR3]ϩ, probably
generated in the ionization process of the aggregates present
in the solid (below). Not surprisingly, therefore, cations [Au-
(PR3)2]ϩ are also present in the spectra with significant intensity.
Of the remaining compounds, only 5 and 9 were sufficiently
soluble to allow useful mass spectra to be obtained. Compound
5 showed a molecular ion in the negative FAB mass spectrum at
m/z 503, however 9 displayed no molecular ion but gave a peak
at m/z 722 for [M Ϫ SC6H4CO2H]ϩ.
Compounds 2–4 could be obtained as single crystals from
chloroform or dichloromethane through layering with pentane,
however 1, 7 and 9 failed to yield crystals of sufficient quality.
The complexes 5, 6 and 8 are insoluble in all common labor-
atory solvents apart from dimethyl sulfoxide and did not yield
crystals suitable for structural analysis.
Fig. 1 Molecular structure of the monomeric unit of complex 2
(ORTEP, 50% probability ellipsoids, hydrogen atoms omitted except for
carboxylic acid) and atomic numbering. Selected bond lengths [Å] and
angles [Њ]: Au–P 2.268(1), Au–S 2.313(1), P–C11 1.824(4), P–C31
1.817(4), P–C51 1.816(4) and S–C1 1.761(4); P–Au–S 176.57(4),
C11–P–C31 105.6(2), C31–P–C51 106.2(2), C11–P–C51 103.9(2) and
Au–S–C1 104.5(1).
Structural studies
Crystals of compound 2 (obtained from dichloromethane–
pentane) are monoclinic, of space group P21/n, with Z = 4
formula units in the unit cell. There are no solvent molecules in
the lattice. The individual mononuclear units (Fig. 1) form
chains along the c axis of the crystal and show contacts between
Au–S groups at one end and paired hydrogen bonding of the
carboxylic acid groups at the other (Fig. 2).
The coordination of the gold atoms in compound 2 is close
to linear [P–Au–S 176.57(4)Њ] and the Et3P–Au–S units of
neighbouring molecules are aligned head to tail to form
parallelograms with edges Au–S 2.313(1), Au ؒ ؒ ؒ S* 3.565(1)
Å and a diagonal Au ؒ ؒ ؒ Au* of 3.629(1) Å. The intermolecular
Au ؒ ؒ ؒ Au* contacts are therefore of about the same length as
the intermolecular Au ؒ ؒ ؒ S* contacts. Since the sum of the van
Fig. 2 Chains of molecules 2 joined together through Au ؒ ؒ ؒ SЈ/
Au ؒ ؒ ؒ AuЈ interactions and through carboxylic hydrogen bonding.
der Waals radii is larger for two gold atoms [3.60 Å] than for an
AuS pair [3.35 Å], the former contact is more likely to be the
dominating contributor to the aggregation. The hydrogen
bonding between the two carboxylic acid groups shows no
structural anomaly.
Crystals of compound 3 (from dichloromethane–pentane)
¯
are triclinic, of space group P1, with Z = 4 mononuclear units
and two molecules of dichloromethane. There is also some as
J. Chem. Soc., Dalton Trans., 2001, 1058–1062
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Fig. 5 Two complex molecules 4 linked by paired hydrogen bonds.
The two monomers (with gold atom Au1) are related by a centre of
inversion (ORTEP, hydrogen atoms omitted except for carboxylic
acids). The lattice contains a second independent molecule (with gold
atom Au2) with similar dimensions and conformations. Selected bond
lengths [Å] and angles [Њ]: Au1–P1 2.256(1), Au1–S1 2.304(1), S1–C11
1.751(4), Au2–P2 2.259(1), Au2–S2 2.308(1) and S2–C21 1.760(4);
P1–Au1–S1 178.40(4), Au1–S1–C11 108.4(1), P2–Au2–S2 177.63(4)
and Au2–S2–C21 107.2(1).
Fig. 3 Molecular structures of two crystallographically independent
complexes 3 joined via aurophilic interactions Au1 ؒ ؒ ؒ Au2 in 3ؒ
0.5CH2Cl2 (details as in Fig. 1). Selected bond lengths [Å], bond angles
and torsion angles [Њ]: Au1 ؒ ؒ ؒ Au2 3.0756(2), Au1–P1 2.276(1), Au1–S1
2.315(1), S1–C1 1.765(4), Au2–P2 2.262(1), Au2–S2 2.302(1) and S2–C8
1.751(4); P1–Au1–S1 168.95(4), Au1–S1–C1 108.6(1), P2–Au2–S2
174.78(4) and Au2–S2–C8 114.4(1); S1–Au1–Au2–S2 117.19(4) and
P1–Au1–Au2–P2 105.08(4).
Fig. 6 Association of the dinuclear units shown in Fig. 5 into chains
through Au1 ؒ ؒ ؒ S1Ј/Au1Ј ؒ ؒ ؒ S1 interactions. Similar chains are formed
from the second set of independent units with gold atom Au2 (see text).
gold atom is attached to a sulfur atom and has coordination
number 2 with only a slight bending of the P–Au–S axes [P1–
Au1–S1 178.40(4), P2–Au2–S2 177.63(4)Њ]. The carboxylic acid
functions are virtually coplanar with the benzene rings. Each
individual monomer [4(I) or 4(II)] is associated with another
monomer of its kind related by a crystallographic centre of
inversion through hydrogen bonding where the two paired
carboxylic acid groups meet. This part is again virtually identi-
cal for the two independent molecules (Fig. 5 shows only the
molecules with P1–Au1–S1).
Similar to the situation found in compound 2, the dimers
generated through hydrogen bonding are aggregated further
into strings of dimers through Au ؒ ؒ ؒ S/Au ؒ ؒ ؒ S contacts at
both ends. Au2S2 parallelograms are formed which are similar
for molecules 4(I) and 4(II) but very different from those found
in 2. The variations arise from a different shifting of the S–Au–
P units against each other. The intra- and inter-molecular Au–
S/Au–S* edges are Au1–S1 2.304(1), Au1 ؒ ؒ ؒ S1* 3.212(1) and
Au2–S2 2.308(1), Au2 ؒ ؒ ؒ S2* 3.253(1) Å but the two Au atoms
are at the ends of the long diagonals [Au1 ؒ ؒ ؒ Au1* 4.234(1),
Au2 ؒ ؒ ؒ Au2* 4.232(1) Å] as compared to Au ؒ ؒ ؒ Au* 3.629(1) Å
in 2.
Fig. 4 Macrocyclic tetranuclear unit of complex 3 in the crystal of
3ؒ0.5CH2Cl2. The monomeric units are joined via aurophilic and paired
hydrogen bonding. Atoms are related by a centre of inversion.
yet unidentified additional solvent in the lattice, which was
disregarded in the refinement of the structure by pertinent
techniques (see Experimental section). The asymmetric unit
contains two independent mononuclear units [3(I), 3(II)] with
very similar molecular geometry. These two units form dimers
via a short intermolecular aurophilic contact [Au1 ؒ ؒ ؒ Au2
3.0756(2) Å] between crossed P–Au–S moieties [S1–
Au1 ؒ ؒ ؒ Au2–S2 117.2Њ] (Fig. 3). Note that in compound 3 the
intermolecular S1 ؒ ؒ ؒ S2 distance [4.562 Å] is much longer than
the Au1 ؒ ؒ ؒ Au2 contact. The crossed arrangement of the
P–Au–S units is necessary in order to accommodate the two
bulky Ph3P groups next to each other. In a parallel organization
(head-to-tail and in particular head-to-head) no short
Au1 ؒ ؒ ؒ Au2 contact would be possible and the system would
probably have to undergo a shift of the units similar to that
detected in compound 2 to entertain at least Au ؒ ؒ ؒ S contacts.
Through the dimerization of the two molecules the two
benzoic acid units become stacked on top of each other, how-
ever the phenylene rings are not coplanar and have a distance
between their centres of 4.041 Å. The carboxylic acid end
groups are able to engage in parallel paired hydrogen bonding
with another dinuclear unit. The distance between the stacked
hydrogen-bonded systems is 3.617 Å and thus shorter than the
distance between the stacked phenylene units (Fig. 4). In total
the compound forms tetramers through a large elongated
macrocycle comprising two pairs of gold atoms and two pairs
of thiolato benzoic acid groups. By contrast, the equivalent
units of compound 2 form a polymer.
In total, compound 4 has two independent polymeric chains
running parallel with only slightly different coupling patterns at
the Au–S end groups. Only one of the two strands is shown in
Fig. 6.
Experimental
General information
The experiments were carried out routinely in air. NMR:
JEOL GX 400 spectrometer using deuteriated solvents with the
usual standards at 25 ЊC. MS: Varian MAT311A instrument
(FAB, p-nitrobenzyl alcohol). The 4-sulfanylbenzoic acid was
obtained commercially. The complexes Au(R3P)Cl (R = Me,14
Et15 or Ph14), Au[(2-NC5H4)Ph2P]Cl,16 (AuCl)2(dppb),17 [N-
(PPh3)][AuCl2],18 Au(Ph P᎐S)Cl,19 (AuCl)2(dppf)20 and [(Ph3-
Crystals of compound 4 (from chloroform) are triclinic, of
¯
space group P1, with Z = 4 molecules of the complex and two
molecules of chloroform in the unit cell. The asymmetric unit
features two independent gold() complexes [4(I), 4(II)] which
are very similar in their dimensions and conformations. Each
᎐
3
PAu)3O]BF421 were prepared following literature procedures.
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J. Chem. Soc., Dalton Trans., 2001, 1058–1062

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Preparations
[Au(4-SC6H4CO2H)]2(dppf) 6. Using the same procedure as
for compound 5 with 4-sulfanylbenzoic acid (30 mg, 0.20
mmol), sodium methoxide (12 g, 0.22 mmol) and (AuCl)2(dppf)
(100 mg, 0.10 mmol) provided a pale yellow product. Yield:
Au(Me3P)(4-SC6H4CO2H) 1. A solution of 4-sulfanylbenzoic
acid (25 mg, 0.16 mmol) and sodium methoxide (9 mg, 0.17
mmol) in methanol (5 mL) was added dropwise to a stirred
solution of Au(Me3P)Cl (50 mg, 0.16 mmol) in dichloro-
methane (15 mL). After stirring for 2 h, all solvent was removed
under vacuum. The residue was dissolved in dichloromethane
(10 mL) and filtered through diatomaceous earth to remove
NaCl. Pentane (25 mL) was added to precipitate the colourless
product in 72% (50 mg) yield. MS (FAB): m/z = 700, 34,
[M ϩ PMe3]ϩ; 427, 60, [M]ϩ; 350, 19, [Au(PMe3)2]ϩ; and 273,
100%, [M Ϫ SC6H4CO2H]ϩ. 31P-{1H} NMR (CD2Cl2): δ 0.86
(s). 1H NMR (d6-dmso): δ 1.61 (d, 9 H, CH3, JHP = 10.2); 7.56,
7.75 (AB system, 4 H, C6H4, JHH = 8.5 Hz). Calc. for
C10H14AuO2PS: C, 28.18; H, 3.31%. Found: C, 27.39; H,
3.48%.
1
66% (81 mg). 31P-{1H} NMR (d6-dmso): δ 32.5 (s). H NMR
(d6-dmso): δ 4.37, 4.58 (m × 2, 8 H, C5H4); 7.50–7.61 (m, 28 H,
C6H5 ϩ C6H4). Calc. for C48H38Au2FeO4P2S2: C, 45.95; H,
3.05%. Found: C, 45.53; H, 2.96%.
[N(PPh3)2][Au(4-SC6H4CO2H)2] 7. A solution of 4-sulfanyl-
benzoic acid (71 mg, 0.46 mmol) and sodium methoxide
(27 mg, 0.50 mmol) in methanol (5 mL) was added dropwise to
a stirred solution of [N(PPh3)2][AuCl2] (150 mg, 0.23 mmol) in
dichloromethane (20 mL) causing immediate precipitation of
a colourless product. After stirring for 1 h, all solvent was
removed under vacuum. The residue was filtered off, washed
with water (30 mL), acetone (10 mL) and pentane (10 mL) to
give a 77% (150 mg) yield. MS (FAB, negative ion): m/z = 503,
100% [M]Ϫ. 31P-{1H} NMR (d6-dmso): δ 20.9 (s, N(PPh3)2). 1H
NMR (d6-dmso): δ 7.46–7.70 (m, 38 H, C6H5 ϩ C6H4). Calc.
for C50H40AuNO4P2S2: C, 57.64; H, 3.87, N, 1.34%. Found: C,
57.00; H, 3.95, N, 1.28%.
Au(Et3P)(4-SC6H4CO2H) 2. Using the same procedure as for
compound 1 with 4-sulfanylbenzoic acid (44 mg, 0.29 mmol),
sodium methoxide (16 g, 0.30 mmol) and Au(Et3P)Cl (100
mg, 0.29 mmol) gave a colourless product. Yield: 67% (90 mg).
MS (FAB): m/z = 784, 4, [M ϩ PEt3]ϩ; 469, 12, [M]ϩ; 434, 2,
[Au(PEt3)2]; and 315, 20%, [M Ϫ SC6H4CO2H]ϩ. 31P-{1H}
NMR (CD2Cl2): δ 38.9 (s). 1H NMR (CD2Cl2): δ 1.23 (dt, 6 H,
CH2, JHP = 18.7, JHH = 7.6); 1.90 (dq, 9 H, CH3, JHP = 9.9 Hz,
JHH = 7.7); 7.57, 7.76 (AB system, 4 H, C6H4, JHH = 8.6 Hz).
Calc. for C13H20AuO2PS: C, 33.34; H, 4.31%. Found: C, 32.99;
H, 4.30%.
Au(Ph P᎐S)(4-SC H CO H) 8. A solution of 4-sulfanyl-
᎐
3
6
4
2
benzoic acid (23 mg, 0.15 mmol) and sodium methoxide (9 mg,
0.17 mmol) in methanol (5 mL) was added dropwise to a stirred
solution of Au(Ph P᎐S)Cl (80 mg, 0.15 mmol) in dichloro-
᎐
3
methane (10 mL) causing immediate precipitation of a colour-
less product. Treatment as for compound 7 gave a 75% (73 mg)
yield. 31P-{1H} NMR (d6-dmso): δ 42.7 (s). 1H NMR (d6-dmso):
δ 7.56–7.70 (m, 19 H, C6H5 ϩ C6H4). Calc. for C25H20AuO2PS2:
C, 42.81; H, 3.04%. Found: C, 42.13; H, 2.80%.
Au(Ph3P)(4-SC6H4CO2H) 3. Using the same procedure as for
compound 1 with 4-sulfanylbenzoic acid (156 mg, 1.01 mmol),
sodium methoxide (60 mg, 1.11 mmol) and Au(Ph3P)Cl (500
mg, 1.01 mmol) provided a colourless product. Yield: 92%
(570 mg). MS (FAB): m/z = 1073, 16, [M ϩ PPh3]ϩ; 722, 9,
[Au(PPh3)2]ϩ; 614, 38, [M]ϩ; and 460, 100%, [M Ϫ SC6H4-
CO2H]ϩ. 31P-{1H} NMR (CDCl3): δ 40.0 (s). 13C-{1H} NMR
(CDCl3): δ 172.0 (s, CO2), 152.3 (s, SC), 134.2 (d, o/m-C of
C6H5, JCP = 13.8), 132.0 (s, o/m-C of C6H4), 131.9 (d, p-C of
C6H5, JCP = 2.3), 129.7 (s, o/m-C of C6H4), 129.3 (d, o/m-C of
[(Ph3PAu)2(4-SC6H4CO2H)]BF4 9. A solution of 4-sulfanyl-
benzoic acid (14 mg, 0.09 mmol), [(Ph3PAu)3O]BF4 (200 mg,
0.14 mmol) and NaBF4 (50 mg, 0.46 mmol) in dichloromethane
(5 mL) was stirred for 2 h. It was filtered and pentane (20 mL)
carefully added to the filtrate to precipitate a colourless product
in 69% (163 mg) yield. MS (FAB): m/z = 722, 56, [M Ϫ SC6H4-
CO2H]; and 459, 85, [Au(PPh3)]ϩ. 31P-{1H} NMR (CDCl3):
1
C6H5, JCP = 11.5) and 129.1 (d, ipso-C6H5, JCP = 58.4 Hz). H
1
δ 35.2 [s(br)]. H NMR (CDCl3): δ 7.33–7.51, 7.57–7.60 (m,
NMR (CDCl3): δ 7.47–7.59 (m, 15 H, C6H5), 7.67, 7.81 (AB
system, 4 H, C6H4, JHH = 8.4 Hz). Calc. for C25H20AuO2PS: C,
49.03; H, 3.29%. Found: C, 49.07; H, 3.32%.
30 H, C6H5), 7.78, 8.08 (AB system, 4 H, C6H4, JHH = 8.4 Hz).
Calc. for C43H35Au2BF4O2P2S: C, 44.58; H, 3.05%. Found: C,
44.56; H, 3.20%.
Au[(2-NC5H4)Ph2P](4-SC6H4CO2H) 4. Using the same
procedure as for compound 1 with 4-sulfanylbenzoic acid (31
mg, 0.20 mmol), sodium methoxide (12 mg, 22 mmol) and
[Au[(2-NC5H4)Ph2P]Cl] (100 mg, 0.20 mmol) provided a
colourless product. Yield: 81% (100 mg). MS (FAB): m/z =
1075, 9, [M ϩ P(C5H4N)Ph2]ϩ; 724, 5, [Au{P(C5H4N)Ph2}2]ϩ;
615, 26, [M]ϩ; and 461, 68%, [M Ϫ SC6H4CO2H]ϩ. 31P-{1H}
NMR (CD2Cl2): δ 39.2 (s). 1H NMR (CD2Cl2): δ 7.40–7.85 (m,
17 H, C6H5 ϩ C6H4) and 8.82 (d, C5H4N, 1 H, JHH = 4.7 Hz).
Calc. for C24H19AuNO2PS: C, 46.99; H, 3.12; N, 2.28%. Found:
C, 46.59; H, 3.17; N, 2.14%.
X-Ray crystallography
Specimens of suitable quality and size of compounds 2, 3, and
4 were mounted on the ends of quartz fibres in F06206R oil and
used for intensity data collection on a Nonius DIP2020
diffractometer employing graphite-monochromated Mo-Kα
radiation. Intensity data were corrected for absorption effects
(DELABS from PLATON).23 The structures were solved by a
combination of direct methods (SHELXS 97)23 and Fourier-
difference syntheses and refined by full matrix least-squares
calculations on F2 (SHELXL 97).24 The thermal motion was
treated anisotropically for all non-hydrogen atoms. All C-H
atoms were calculated and allowed to ride on their parent atoms
with fixed isotropic contributions, whereas all O-H atoms were
located and refined isotropically. Crystals of compound 3 con-
tained some additional disordered and unidentified solvent in
the lattice which was not included in the refinement but was
handled using the ‘SQUEEZE’ procedure (from PLATON).22
The volume occupied by the solvent is 112 Å3, and the
number of electrons per unit cell deduced by SQUEEZE is
19 corresponding to half-occupancy by disordered dichloro-
methane or tetrahydrofuran. Further information on crystal
data, data collection and structure refinement is summarized
in Table 1.
[Au(4-SC6H4CO2H)]2(dppb) 5. A solution of 4-sulfanyl-
benzoic acid (51.9 mg, 0.34 mmol) and sodium methoxide
(20 mg, 0.37 mmol) in methanol (5 mL) was added dropwise
to a stirred solution of (AuCl)2(dppb) (150 mg, 0.17 mmol) in
dichloromethane (15 mL) causing immediate precipitation of
a colourless product. After stirring for 1 h, all solvent was
removed under vacuum. The residue was filtered off, washed
with water (25 mL), acetone (10 mL) and pentane (10 mL) to
give a 60% (113 mg) yield. 31P-{1H} NMR (d6-dmso): δ 36.2 (s).
1H NMR (d6-dmso): δ 1.76 [s(br), 4 H, CH2], 2.84 [s(br), 4 H,
CH2], 7.50, 7.64 (AB system, 8 H, C6H4, JHH = 8.4 Hz); 7.55,
7.74–7.80 (m, 20 H, C6H5). Calc. for C21H19AuO2PS: C, 44.77;
H, 3.40%. Found: C, 44.28; H, 3.37%.
CCDC reference numbers 155654–155656.
J. Chem. Soc., Dalton Trans., 2001, 1058–1062
1061

View Article Online
Table 1 Crystal data, data collection and structure refinement for compounds 2, 3ؒ0.5CH2Cl2 and 4ؒ2CHCl3
2
3ؒ0.5CH2Cl2
4ؒ2CHCl3
Empirical formula
M
C13H20AuO2PS
468.29
C25.50H21AuClO2PS
654.87
C25H20AuCl3NO2PS
732.77
Crystal system
Space group
Monoclinic
P21/n
Triclinic
P1
Triclinic
P1
¯
¯
a/Å
b/Å
c/Å
α/Њ
7.2190(1)
14.0220(1)
15.4040(1)
12.0102(2)
13.3450(3)
17.0602(3)
74.062(1)
71.819(1)
86.963(1)
2496.37(8)
4
8.3563(1)
17.4820(3)
19.2000(3)
104.530(1)
90.423(1)
102.696(3)
2642.92(7)
4
β/Њ
93.094(5)
γ/Њ
U/Å3
1556.99(3)
4
96.8
143
Z
µ(Mo-Kα)/cmϪ1
T/K
61.68
143
60.3
143
Measured reflections
Unique reflections
Refined parameters
R1 [I > 2σ(I)]
wR2
26047
4807 [Rint = 0.0427]
163
0.0313
0.0707
36359
9408 [Rint = 0.0335]
576
0.0266
0.0629
59270
15978 [Rint = 0.0531]
621
0.0420
0.0884
Schmidbaur, Inorg. Chem. Commun., 1998, 1, 115; K. Nomiya,
N. C. Kasuga, I. Takamori and K. Tsuda, Polyhedron, 1998, 17,
3519; J.-C. Shi, B.-S. Kang and T. C. W. Mak, J. Chem. Soc., Dalton
Trans., 1997, 2171; J. Vicente, M. T. Chicote, M. D. Abrisqueta,
R. Guerro and P. G. Jones, Angew. Chem., Int. Ed. Engl., 1997, 36,
1203; D. M. P. Mingos, J. Yau, S. Menzer and D. J. Williams,
J. Chem. Soc., Dalton Trans., 1995, 319; P. D. Cookson and E. R. T.
Tiekink, J. Coord. Chem., 1992, 26, 313.
7 W. Schneider, A. Bauer and H. Schmidbaur, Organometallics, 1996,
15, 5445; A. Sladek, W. Schneider, K. Angermeier, A. Bauer and
H. Schmidbaur, Z. Naturforsch., Teil B, 1996, 51, 765.
8 S. Esperas, Acta. Chem. Scand., Ser. A, 1976, 30, 527.
9 C. Hollatz, A. Schier and H. Schmidbaur, J. Am. Chem. Soc., 1997,
119, 8115; C. Hollatz, A. Schier, J. Riede and H. Schmidbaur,
J. Chem. Soc., Dalton Trans., 1999, 111.
Seehttp://www.rsc.org/suppdata/dt/b1/b100113m/forcrystal-
lographic data in CIF or other electronic format.
Acknowledgements
Support of this work by the Deutsche Forschungsgemeinschaft,
the Volkswagenstiftung, the Alexander von Humboldt Stiftung
(J. D. E. T. W.-E.), and by the Fonds der Chemischen Industrie
is gratefully acknowledged. The authors are also indebted
to Degussa AG and Heraeus GmbH. for the donation of
chemicals.
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