Mono- and dinuclear gold(I) thio- and selenocyanate complexes

Article abstract of DOI:10.1016/S0020-1693(03)00144-0

Complexes of the type (R₃P)AuSCN and (R₃P)AuSeCN have been prepared in high yields from the corresponding chlorides (R₃P)AuCl by treatment with KSCN or KSeCN, respectively, in a two-phase water/dichloromethane system. Crystal structure determinations revealed discrete monomeric molecules for the isomorphous thiocyanate and selenocyanate compounds with R=2-MeC₆H₄. For R=ⁱPro there is only weak association into dimers via long Au-S contacts, but for R₃=Me₂PhP chain-like polymers are formed via short aurophilic interactions [Au-Au, 3.2334(2) and 3.2533(2) ?]. A monoclinic modification of (Ph₃P)AuSCN was found, which shows a standard geometry of the molecules. An orthorhombic modification published previously featured a doubtful strongly distorted molecular geometry. All compounds of the type (R₃P)AuS/SeCN can be converted into salts with dinuclear cations {[(R₃P)Au]₂S/SeCN}⁺Y^- on reaction with equimolar quantities of [(R₃P)Au]⁺Y^- (Y=BF₄, SbF₆) as confirmed by analytical and spectroscopic data. The S/SeCN units are found to be bridging the two metal atoms via the S/Se atoms. The tetrafluoroborates are less stable than the hexafluoroantimonates, and all selenocyanate complexes are markedly less stable thermally and more sensitive towards air and moisture than their sulfur counterparts.

Full text of DOI:10.1016/S0020-1693(03)00144-0

Inorganica Chimica Acta 352 (2003) 179ꢃ187
/
www.elsevier.com/locate/ica
Mono- and dinuclear gold(I) thio- and selenocyanate complexes
Daniel Schneider, Stefan Nogai, Annette Schier, Hubert Schmidbaur *
Anorganisch-chemisches Institut der Technischen Universitat Munchen, Lichtenbergstrasse 4, D-85747 Garching, Germany
¨ ¨
Received 13 September 2002; accepted 27 September 2002
Dedicated to Prof. Martin Bennett
Abstract
Complexes of the type (R3P)AuSCN and (R3P)AuSeCN have been prepared in high yields from the corresponding chlorides
(R3P)AuCl by treatment with KSCN or KSeCN, respectively, in a two-phase water/dichloromethane system. Crystal structure
determinations revealed discrete monomeric molecules for the isomorphous thiocyanate and selenocyanate compounds with Rꢀ
MeC6H4. For Rꢀi
Pro there is only weak association into dimers via long AuꢀS contacts, but for R3ꢀMe2PhP chain-like polymers
are formed via short aurophilic interactions [AuꢀAu, 3.2334(2) and 3.2533(2) A]. A monoclinic modification of (Ph3P)AuSCN was
/2-
/
/
/
˚
/
found, which shows a standard geometry of the molecules. An orthorhombic modification published previously featured a doubtful
strongly distorted molecular geometry. All compounds of the type (R3P)AuS/SeCN can be converted into salts with dinuclear
cations {[(R3P)Au]2S/SeCN}ꢁYꢂ on reaction with equimolar quantities of [(R3P)Au]ꢁYꢂ (Yꢀ
BF4, SbF6) as confirmed by
/
analytical and spectroscopic data. The S/SeCN units are found to be bridging the two metal atoms via the S/Se atoms. The
tetrafluoroborates are less stable than the hexafluoroantimonates, and all selenocyanate complexes are markedly less stable
thermally and more sensitive towards air and moisture than their sulfur counterparts.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Selenocyanate complexes; Thiocyanate complexes; Gold
1. Introduction
thiourea and thiosulfate, the thiocyanate process has
never become a strong competitor of cyanide leaching.
Gold(I) thiocyanate complexes have also been inves-
tigated as chemotherapeutic agents, including mainly
studies of the anti-tumor and anti-HIV activity, and
cytotoxicity of several tertiary phosphine complexes of
AuSCN [7]. These complexes may also be involved in
the transformation of contemporary gold drugs like
Auranofin† in the human body because of the almost
ubiquitous presence of traces of cyanide and the
metabolic generation of [Au(CN)2]ꢂ [8]. The role and
action of selenocyanate [SeCN]ꢂ has been studied much
less, but the importance of selenium-dependent enzymes
suggests that complexes of AuSeCN may well also play
a significant role in physiological processes involving
traces of gold [9,10].
Gold(I) pseudohalides are among the most important
classes of gold compounds [1]. This is, particularly, true
for gold(I) cyanides which are not only key intermedi-
ates for recovery and recycling of gold [2], but also for
gold plating [3] and gold surface technology [4]. The
cyanide anion [CN]ꢂ has the highest affinity for gold(I)
and leads to the most dramatic changes in the electro-
chemical potential of gold in aqueous solution. In this
respect, it exceeds even sulfide [S]2ꢂ, hydrogensulfide
[SH]ꢂ and thiocyanate anions [SCN]ꢂ which give rise
to stability constants not very different from the cyanide
extreme [5]. Gold extraction processes have also been
probed with thiocyanate as a leaching agent, which may
have technological and environmental advantages over
cyanide [6], however, like technologies employing
The literature on the complexes of the type
(R3P)AuSCN [11ꢃ27] is quite extensive, but for
/
(R3P)AuSeCN [10,13,14,16] it remained rather limited
(Table 1), and structural data are available only for
isolated cases. As a continuation of recent studies [11],
* Corresponding author. Tel.: ꢁ
13125.
E-mail address: h.schmidbaur@lrz.tum.de (H. Schmidbaur).
/
49-89-289 13130; fax: ꢁ49-89-289
/
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00144-0

180
D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ187
/
Table 1
Gold(I) thiocyanate and selenocyanate complexes with mono-, bi- and
tridentate tertiary phosphine ligands
convenient synthesis (Eqs. (1) and (2)) gives pure
products as colourless solids in high yields.
(R3P)AuClꢁKSCN 0 KClꢁ(R3P)AuSCN
For 1: RꢀPh; 2: Rꢀ2-MeC6H4; 3: Rꢀ
4: R3ꢀ Pro.
Me2Ph; 5: Rꢀi
(1)
Complex
Literature
/
/
/
3-MeC6H4;
Monodentate ligands
(Me3P)AuSCN
(Et3P)AuSCN
[(iPr)3P]AuSCN
/
/
[11ꢃ14]
/
[12,15]
[12], this work
(R3P)AuClꢁKSeCN 0 KClꢁ(R3P)AuSeCN
For 6: RꢀPh; 7: Rꢀ2-MeC6H4; 8: R3 ꢀMe2Ph:
(2)
(Ph3P)AuSCN
[12ꢃ/14,16ꢃ22], this
/
work
The thiocyanate compounds 1ꢃ3 with bulky triaryl-
/
[(2-MeC6H4)3P]AuSCN
[(3-MeC6H4)3P]AuSCN
[(4-MeC6H4)3P]AuSCN
[(4-ClC6H4)3P]AuSCN
this work
this work
[17]
phosphines are very stable and show no decomposition
at room temperature in the laboratory atmosphere and
in daylight. The alkylphosphine thiocyanate complexes
4 and 5 are air-sensitive, but can be kept in sealed vessels
at room temperature. By contrast, all selenocyanate
[17,23]
[12]
[13,14]
[(2-CNꢀC2H4)3P]AuSCN
/
[(PhO)3P]AuSCN
(Me2PhP)AuSCN
(MePh2P)AuSCN
(EtPh2P)AuSCN
[(4-MeC6H4)Ph2P]AuSCN
(Et3P)AuSeCN
[24], this work
[24]
[17,24]
complexes 6ꢃ8 are thermolabile as solids and in solu-
/
tion, and must be stored at low temperature in the dark.
Exposed to air the compounds decompose rapidly with
formation of red elemental selenium.
[12]
[10]
(Ph3P)AuSeCN
[13,14,16], this
work
The compounds have been identified by elemental
analyses, mass spectrometry, and their IR and NMR
[(2-MeC6H4)3P]AuSeCN
(Me2PhP)AuSeCN
this work
this work
spectroscopic characteristics. The thiocyanates 1ꢃ5
/
show intense absorptions for the n(CN) stretching
vibration shifted very significantly to higher wavenum-
Bidentate ligands
NCSAu[(Ph2P)-CH2-(PPh2)]AuSCN
[24]
bers (2110ꢃ
2130 cmꢂ1) as compared with free [SCN]ꢂ:
/
NCSAu[(Ph2P)-CH2-CH2ꢀ
NCSAu[(Et2P)-C6H4-(PEt2)]AuSCN
NCSAu[(Ph2P)-C6H4-(PPh2)]AuSCN
/
(PPh2)]AuSCN
[16,17,24]
[25]
2066 cmꢂ1 [31]. This is indicative of binding of the gold
atom solely to the sulfur/selenium end of the anion. A
weak band detected for all thiocyanate complexes at
[25]
NCSAu[(Ph2P)-CHꢁ
NCSAu[(Ph2P)-CꢂC-(PPh2)]AuSCN
NCSeAu[(Ph2P)-CH2-CH2-(PPh2)]AuSeCN
/
CH-(PPh2)]AuSCN
[24]
[26]
/
2053ꢃ
mode, which is not observed for the selenocyanate
complexes 6ꢃ8 owing to the larger mass of selenium.
/
2075 cmꢂ1 can be assigned to a combination
[16]
Tridentate ligands
/
NSCAu{[(Ph2P)ꢀ
(PPh2)]}-AuSCN
/
CH2ꢀ
/
[(PPh)AuSCN]ꢀ
/
CH2ꢀ
/
[27]
The NMR spectra show only one set of sharp reso-
nances for the PR3 ligand independent of temperature,
which rules out any equilibrium of the type shown in Eq.
Refs. [11,20] indicate structural characterization.
(3). The 31P signals of the thiocyanates 1ꢃ
5 are shifted to
/
we, therefore, investigated a series of representative
complexes, which were expected to provide more
detailed structural data and information on the forma-
tion and general properties of such compounds. Parti-
cular attention was focused on dinuclear species in
which the pseudohalide anion is in a bridging position
between two metal atoms. Results of recent studies of
the corresponding halide complexes have shown that
these dinuclear compounds may aggregate further to
lower fields by about 5 ppm as compared with the
corresponding chloride complexes, while for the seleno-
cyanates 6ꢃ8 an additional low-field shift of only less
/
than 1.5 ppm is observed. The 13C signals of the anions
were not detected.
2(R3P)AuSCN?[(R3P)2Au]ꢁ[Au(SCN)2]ꢂ
(3)
The FAB mass spectra of all complexes showed the
protonated molecular ion, but the ions of highest
abundance were the fragments [(R3P)Au]ꢁ and the
redistribution products [(R3P)2Au]ꢁ and {[(R3P)Au]2S/
SeCN}ꢁ. This observation is in agreement with results
give larger clusters [28ꢃ30].
/
2. Preparative results
obtained with halide complexes [(R3P)AuX] (XꢀCl, Br,
/
I) where cations {[(R3P)Au]2X}ꢁ are observed with
high abundance. The results suggest that dinuclear thio/
selenocyanate complexes are readily formed and of high
stability as isolated species in the gas phase.
In previous studies, the synthesis of complexes of the
general type (R3P)AuSCN and (R3P)AuSeCN was
carried out as a heterogeneous process in a non-aqueous
solvent. As recently demonstrated [11,25,27], there is
great advantage in a preparation in a two-phase system
with an alkali thiocyanate dissolved in water and a
(phosphine)gold(I) halide in dichloromethane. This
Preparative attempts confirmed these expectations.
Treatment of compounds (R3P)AuS/SeCN with equi-
molar quantities of [(R3P)Au]BF4 or [(R3P)Au]SbF6*
/
prepared in situ*in dichloromethane at ꢂ78 8C gave
/
/

D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ
/187
181
the dinuclear adducts in high yield (Eqs. (4) and (5)).
cation is the dominant species in the high-mass region of
the spectra of the hexafluoroantimonate salts, while for
the mononuclear compounds it was only a minor
component probably formed upon bombardment and
ionization of the samples.
Although no single crystals could be grown for any of
the tetrafluoroborate or hexafluoroantimonate salts, the
spectroscopic and analytical data provide sufficient
evidence for the products proposed in Eqs. (4) and (5).
The results are also in agreement with previous work,
where a different preparative approach had been chosen
(R3P)AuSCNꢁ[(R3P)Au]Y
ꢁ
0 f[(R3P)Au]2SCNg Yꢂ
(4)
SbF6; 11:
3-MeC6H4, Yꢀ
For 9: Rꢀ
Rꢀ2-MeC6H4, Yꢀ
SbF6; 13: R3ꢀMe2Ph; Yꢀ
SbF6.
/
Ph, Yꢀ
/
BF4; 10: Rꢀ
/
Ph, Yꢀ
/
/
/
SbF6; 12: Rꢀ
/
/
/
/
SbF6; 14: Rꢀi
/
Pro, Yꢀ
/
(R3P)AuSeCNꢁ[(R3P)Au]SbF6
ꢁ
0 f[(R3P)Au]2SeCNg [SbF6]ꢂ
(5)
[22,28ꢃ30].
/
For 15: RꢀPh; 16: R3 ꢀMe2P; 17: Rꢀ2-MeC6H4:
The thiocyanates are colourless solids which are
soluble in polar solvents like dichloromethane, tetrahy-
drofuran or chlorobenzene, but insoluble in pentane or
diethylether. The tetrafluoroborate salt 9 proved to be
much less stable as a solid and in solution against air
and light than the hexafluoroantimonate 10 and, there-
fore, for all other preparations only the hexafluoroanti-
3. Structural investigations
(Triphenylphosphine)gold thiocyanate (1) was ob-
tained in an orthorhombic form in a previous study by
Barron et al. [20]. The structure was solved with low
precision and gave a molecular geometry with unex-
monates were chosen (10ꢃ17). The sterically protected
/
pected distorsions, in particular an angle Sꢀ
/
Cꢀ
/
N of
˚
C of 1.36(2) A.
compounds 11 and 12 are again found to be most stable
and the solids can be handled in air and daylight.
However, solutions are very unstable and decomposi-
tion is observed already after a few minutes at room
temperature.
161(3)8 and a distance Sꢀ
In our own experiments a monoclinic form, space
group P21/c (Zꢀ2), was isolated from an solution
/
/
containing (Ph3P)AuCl. The structure could be refined
on a perfectly satisfactory level and gave a molecular
geometry, which meets the expectations. The distances
The selenocyanates 15ꢃ/17 are very unstable and were
found to decompose rapidly already above ꢂ
/
40 8C. The
Au1ꢀ
/
P1, Au1ꢀ
/
S1 and S1ꢀ
/
C1 are 2.2542(13), 2.3312(15)
˚
and 1.614(9) A, respectively, are in the range established
by earlier investigations of (phosphine)gold sulfur
compounds were characterized only tentatively on the
basis of their solution NMR and solid state IR data (see
Section 4). Red selenium and yellow gold(I) cyanide
appear as the decomposition products in solution and in
solids isolated from the reaction mixture by evaporation
compounds. The angle S1ꢀ
to linear.
The molecules are loosely aggregated into pairs
/
C1ꢀN1 of 177.1(1)8 is close
/
˚
of all volatiles at ꢂ
Solutions of compounds 9ꢃ
show 31P singlet resonances which are shifted upfield
from the signals of the precursor molecules 1ꢃ5 by
/
78 8C.
through long Auꢀ
/
S contacts (Au1ꢀS1?, 3.495 A) which
/
/
14 in CD2Cl2 at ꢂ50 8C
/
are reminiscent of the structure of (Me3P)AuSCN [11]
(Fig. 1).
/
approximately 3.6 (9, 10), 4.1 (11), 2.2 (12, 14) and 4.4
ppm (13). The effects observed for the resonances of the
organic substituents are only marginal. The IR spectra
exhibit shifts of the n(CN) stretching frequency to
higher wavenumbers by up to 35 cmꢂ1 (9ꢃ
13). This
/
displacement is in agreement with a model in which the
sulfur atom of the thiocyanate group is h2-coordinated
to two metal atoms. For N-coordination of the second
gold atom a shift in the opposite direction is to be
expected. The 31P NMR and IR data of 15 are similar to
those of 10 suggesting analogous effects of the com-
plexation.
Mass spectra (FAB) could only be obtained for the
compounds with aryl substituents (9ꢃ12). The spectra
/
show the cations {[(R3P)Au]2SCN}ꢁ as the peaks of
highest mass followed by [(R3P)2Au]ꢁ and [(R3P)Au]ꢁ.
It should be remembered that the same series of peaks
Fig. 1. Molecular structure of (Ph3P)AuSCN (1) (ORTEP, 50%
probability ellipsoids). The monomers are loosely aggregated into
˚
dimers with long Au-S contacts of 3.495 A. Selected structural
parameters: Au-S 2.3312(15), Au-P 2.2542(13), S-C 1.614(9) and C-
˚
was also observed for the precursor molecules 1ꢃ
/
3, but
N
1.203(10) A, P-Au-S 177.88(6)8, Au-S-C 95.4(2)8 and S-C-N
with entirely different intensity ratios. The dinuclear
177.4(6)8.

182
D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ187
/
The two complexes 2 and 7 with bulky (2-MeC6H4)3P
ligands are expected to have simple mononuclear
structures because steric hindrance rules out any close
approach of the metal atoms. This expectation is
confirmed by the single crystal structure investigations.
The orthorhombic crystals of the sulfur (2) and selenium
compound (7) are isomorphous of space group Pbca
(Zꢀ8) with very similar unit cell geometries (Table 2).
/
The lattices contain isolated molecules (Figs. 2 and 3)
with no sub-van der Waals contacts. The tertiary
phosphines have a propeller-type arrangement of the
three ortho-tolyl groups very common for this ligand in
any of its complexes. The configuration of the metal
atom is close to linear with P1ꢀ
P1ꢀAu1ꢀSe1 176.90(2)8. The angles at the chalkogen
atoms are acute with Au1ꢀS1ꢀC1 98.75(11)8 and Au1ꢀ
Se1ꢀC1 96.73(11)8 while the angle at the internal carbon
atom of the pseudohalide group is again close to linear:
S1ꢀC1ꢀN1 177.1(3)8 and Se1ꢀC1ꢀN1 177.2(3)8. Sig-
nificant differences are found for the distances Au1ꢀS1
Se1 2.4259(3)/Se1ꢀ
/
Au1ꢀS1 176.90(3)8 and
/
Fig. 2. Molecular structure of [(2-MeC6H4)3P]AuSCN (2) (ORTEP,
50% probability ellipsoids). Selected structural parameters: Au-S
˚
2.3256(8), Au-P 2.2726(7), S-C 1.681(3) and C-N 1.147(4) A, P-Au-S
/
/
/
/
/
/
176.90(3)8, Au-S-C 98.75(11)8 and S-C-N 177.1(3)8.
/
/
/
/
/
Seꢀ
/
C) are not the same. It appears that the Auꢀ
/Se bond
2.3256(8)/S1ꢀ
/
C1 1.681(3) and Au1ꢀ
C1 1.843(4) A, which reflect the increasing covalent
/
/
˚
is, particularly, short which may reflect the high affinity
of gold for selenium (and tellurium!). All other dimen-
sions in 2 and 7 show only minor variations.
radius of selenium as compared with sulfur. Note that
˚
S/Se and 0.162 A for S/
the differences (0.100 for Auꢀ
/
Table 2
Crystal data, data collection, and structure refinement
Ph3PAuSCN (1)
(o-Tol)3PAuSCN (2)
Me2PhPAuSCN (4)
(iPro)3PAuSCN (5) (o-Tol)3PAuSeCN (7)
Crystal data
Empirical formula
Mr
C
19H15AuNPS
C22H21AuNPS
559.39
orthorhombic
Pbca
C9H11AuNPS
393.18
C10H21AuNPS
415.27
monoclinic
P21/c
C22H21AuNPSe
606.29
orthorhombic
Pbca
516.96
monoclinic
P21/c
Crystal system
Space group
monoclinic
P21/n
˚
a (A)
9.3287(3)
17.3955(5)
11.4669(4)
90
14.9490(1)
16.2360(1)
16.1510(2)
90
11.6485(1)
12.2737(1)
16.3318(2)
90
7.9085(1)
8.4179(1)
21.1214(3)
90
15.0130(1)
16.2840(1)
16.3170(2)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
105.889(1)
90
90
90
105.809(1)
90
99.271(1)
90
90
90
3
˚
V (A )
1789.7(1)
1.920
3920.0(1)
1.896
2246.7(1)
2.325
1387.8(1)
1.988
3988.5(1)
2.019
rcalc (g cmꢂ3
)
Z
4
984
8
2160
8
1456
4
792
8
2304
F(0 0 0)
m(Mo Ka) (cmꢂ1
Data collection
T (K)
)
84.24
76.99
133.79
108.35
92.88
ꢂ130
/
ꢂ130
/
ꢂ130
/
ꢂ130
/
ꢂ/130
Measured reflections
Unique reflections
Absorption correction
Tmin/Tmax
31160
3963 [Rint
DELABS
159555
0.049] 5810 [Rint
DELABS
86484
6125 [Rint
DELABS
36402
3023 [Rint
DELABS
102754
4391 [Rint
DELABS
ꢀ/
ꢀ/0.054]
ꢀ/0.052]
ꢀ/
0.044]
ꢀ/0.052]
0.461/0.824
208
0.447/0.818
319
0.439/0.814
235
0.428/0.809
127
0.488/0.836
235
Refinement
Refined parameters
Final R values [I ]/2s(I)]
R1
0.0346
0.0814
0.0251
0.0597
0.0294
0.0722
0.0251
0.0647
0.0215
0.0519
a
wR2
(Shift/error)max
Max./min., rfin (e A
B
2.210/ꢂ
/
0.001
B
1.639/ꢂ
/
0.001
B
2.879/ꢂ
/
0.001
B
2.554/ꢂ
/
0.001
B
/
0.001
ꢂ3
˚
)
/
1.398
/
0.932
/
1.744
/
1.125
0.979/ꢂ0.636
/
{[aw(F02ꢂ
/
Fc2)2]/a[w(F02)2]}1/2; wꢀ
/
1/[s2(F02)ꢁ(ap)2ꢁ
/
/
bp]; pꢀ
/
(F02ꢁ2Fc2)/3; aꢀ
0.0000 (1), 0.0107 (2), 0.0364 (4), 0.0234 (5), 0.0073 (7);
/
/
a
wR2ꢀ
/
bꢀ
/
4.49 (1), 8.58 (2), 4.29 (4), 3.06 (5), 8.90 (7).

D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ
/187
183
Fig. 5. Molecular structure of (Me2PhP)AuSCN (4) (ORTEP, 50%
probability ellipsoids). The monomers are aggregated into dimers
˚
through short aurophilic contacts [Au1-Au2, 3.2533(2) A]. Selected
Fig. 3. Molecular structure of [(2-MeC6H4)3P]AuSeCN (7) (ORTEP,
50% probability ellipsoids). Selected structural parameters: Au-Se
˚
2.4259(3), Au-P 2.2781(8), Se-C 1.843(4) and C-N 1.134(5) A; P-Au-
structural parameters: Au1-S1 2.3423(10), Au2-S2 2.3554(13), Au1-P1
2.2618(10), Au2-P2 2.2681(11), S1-C1 1.675(5), S2-C2 1.638(6), C1-N1
Se 176.90(2)8, Au-Se-C 96.73(11)8 and Se-C-N 177.2(3)8.
˚
1.141(7) and C2-N2 1.192(7) A; P1-Au1-S1 176.10(4)8, P2-Au2-S2
Crystals of the tri(ipropyl)phosphine complex 5 are
169.89(4)8, Au1-S1-C1 101.44(16)8, Au2-S2-C2 105.90(19)8, S1-C1-N1
176.7(5)8 and S2-C2-N2 166.9(6)8.
monoclinic, space group P21/c, with Zꢀ4 formula
/
units in the unit cell. The individual molecules are not
completely separated and feature distant intermolecular
between the monomers. Along the meandering chains of
metal atoms there are alternating (but very similar)
contacts between the gold and sulfur atoms (Fig. 4;
˚
Au1ꢀS1? 3.738 A). The two monomers in the aggregate
/
intra- and inter-dimer Au1ꢀ
/
Au2 distances of 3.2334(2)
and 3.2533(2) A. The AuꢀAuꢀAu angles along the
chain of gold atoms are 159.942(5)8 at Au1 and
148.050(5)8 at Au2 with a torsional angle Au2?ꢀAu1ꢀ
Au2ꢀAu1? of 47.847(18)8. The internal dimensions of
the individual molecules show no anomalies except for a
striking difference (108) in the SꢀCꢀN angles for the
two independent molecules: S1ꢀC1ꢀN1 176.7(5), S2ꢀ
C2ꢀN2 166.9(6)8. The angles Au1ꢀS1ꢀC1 101.4(2)8 and
Au2ꢀS2ꢀC2 105.9(2)8 in 4 differ much less (4.58), but
this difference may still be responsible for the variation
in the neighbouring SꢀCꢀN angle. There is no evidence
are related by a center of inversion. This mode of
association is again reminiscent of the structure of
˚
/
/
(Me3P)AuSCN
[179.72(4)8] and S1ꢀ
linear, but the chain of atoms is strongly bent at the
C1 99.51(15)8. All other details
[11].
The
angles
P1ꢀ
/
Au1ꢀ
/
S1
/
/
/
C1ꢀ
/
N1 [177.9(4)8] are almost
/
sulfur atom: Au1ꢀ
/
S1ꢀ
/
/
/
deserve no special comment.
Crystals of the dimethylphenylphosphine complex 4
/
/
/
/
/
/
are also monoclinic, space group P21/n, with Zꢀ8
/
/
/
formula units in the unit cell. The asymmetric unit
contains two independent molecules aggregated via an
aurophilic contact to form a dimer as shown in Fig. 5.
These dimers are further aggregated to give chains as
illustrated in Fig. 6. Clearly, the strongly reduced steric
bulk of the phosphine Me2PhP (as compared with 1, 2,
5, and 7,above) gives sufficient room for close contacts
/
/
for unusual differences in intermolecular contacts of the
two thiocyanate groups in the lattice (Fig. 5).
In the family of (phosphine)gold thiocyanates,
(Me2PhP)AuSCN is only the third case where aurophilic
Fig. 4. Molecular structure of [(Me2CH)3P]AuSCN (5) (ORTEP, 50% probability ellipsoids). The monomers are aggregated loosely into dimers with
˚
˚
long Au-S? contacts of 3.738(6) A. Selected structural parameters: Au-S 2.3276(10), Au-P 2.2696(10), S-C 1.691(5) and C-N 1.151(6) A; P-Au-S
179.72(4)8, Au-S-C 99.51(15)8 and S-C-N 177.9(4)8.

184
D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ187
/
˚
Fig. 6. Aggregation of the dimers shown in Fig. 5 into chains via aurophilic contacts [Au1-Au2? 3.2334(2) A]. Angles and torsional angles of the
chain: Au2-Au1-Au2? 159.942(5)8, Au1-Au2-Au1? 148.050(5)8, Au2?-Au1-Au2-Au1? 47.847(18)8.
1
interactions determine the arrangement of the molecules
in the solid state. A cyclic aggregate was discovered by
Bennett et al. [25].
(83%); m.p., 169 8C. H NMR: dꢀ
/
7.52ꢃ
13.5 Hz, C2/6],
11.9 Hz, C3/5], 128.3
62.8 Hz, C1]. 31P{1H} NMR: dꢀ
37.9 [s,
PPh3]. IR (KBr): 2130 cmꢂ1, s, 2075 cmꢂ1, w, n(CN).
MS (FAB): m/zꢀ
977 (48.6%) {[(Ph3P)Au]2SCN}ꢁ, 721
1]ꢁ, 459 (100)
/
7.58 [m, Ph].
2
13C{1H} NMR: dꢀ
/
134.6 [d, J(C,P)ꢀ
/
3
132.6 [s, C4], 129.8 [d, J(C,P)ꢀ
/
1
[d, J(C,P)ꢀ
/
/
/
4. Experimental
(28.6) [(Ph3P)2Au]ꢁ, 518 (15.6) [Mꢁ
/
[(Ph3P)Au]ꢁ, 262 (6.3) [Ph3P]ꢁ. Anal. Calc. for
C19H15AuNPS (517.34 g molꢂ1): C, 44.1; H, 2.9; N,
2.7. Found: C, 44.0; H, 2.9; N 2.7%.
4.1. General
All experiments were routinely carried out in an
atmosphere of dry nitrogen. Solvents and glassware
were dried and saturated/filled with nitrogen. Standard
equipment was used throughout. The AuCl complexes
4.3. [Tri(2-methylphenyl)phosphine]gold thiocyanate
(2)
were prepared by published methods [32ꢃ37]. All NMR
spectra (d in [ppm], J in [Hz]) were recorded in CD2Cl2
at 23 8C unless otherwise stated.
/
Following the same procedure using 300 mg (0.57
mmol) of [(2-MeC6H4)3P]AuCl and 112 mg (1.14 mmol)
of KSCN; Yield, 255 mg (80%); m.p. (dec.), 225 8C. H
1
NMR: dꢀ
/
6.85ꢃ
/
7.53 [m, 12H, C6H4], 2.70 [s, 9H, Me].
143.3 [d, 2J(C,P)ꢀ
4.2. (Triphenylphosphine)gold thiocyanate (1) [20]
13C{1H} NMR: dꢀ
/
/
14.6 Hz, C2],
3
2
134.1 [d, J(C,P)ꢀ
/
9.2 Hz, C6], 132.9 [d, J(C,P)ꢀ
/
8.5
Solutions of (Ph3P)AuCl (300 mg, 0.61 mmol) in
dichloromethane (12 ml) and of KSCN (127 mg, 1.29
mmol) in water (10 ml) were mixed and stirred
vigorously for 3 h at 20 8C. The aqueous phase was
then separated from the organic phase and extracted
three times with 5 ml portions of CH2Cl2. The combined
organic phases were washed three times with 5 ml
portions of water and dried over MgSO4. The solvent
was evaporated in a vacuum until a precipitate ap-
peared. By addition of pentane (50 ml) and cooling to
3
Hz, C5], 132.6 [s, C4], 127.3 [d, J(C,P)ꢀ
/10.0 Hz, C3],
1
3
125.2 [d, J(C,P)ꢀ
Hz, Me]. 31P{1H} NMR: dꢀ
(KBr): 2120 cmꢂ1, s, 2071 cmꢂ1, w, n(CN). MS (FAB):
m/zꢀ
1061 (7.3%) {[(o-tol)3PAu]2SCN}ꢁ, 806 (15.6)
1]ꢁ, 501 (100) {[(o-
/
59.9 Hz, C1], 23.5 [d, J(C,P)ꢀ
/11.5
/13.1 [s, P(o-tol)3]. IR
/
{[(o-tol)3P]2Au}ꢁ, 560 (53.1) [Mꢁ
/
tol)3P]Au}ꢁ. Anal. Calc. for C22H21AuNPS (559.42 g
molꢂ1): C, 47.2; H, 3.8; N, 2.5; S, 5.7. Found: C, 46.9;
H, 3.8; N, 2.5; S, 5.8%.
ꢂ30 8C overnight the precipitation is complete. After
/
filtration and drying in a vacuum the product was
recrystallized from dichloromethane/pentane. The col-
ourless solid is stable to air and light, and soluble in
CH2Cl2, tetrahydrofuran and chlorobenzene, but inso-
luble in n-pentane and diethylether. Yield, 260 mg
4.4. [Tri(3-methylphenyl)phosphine]gold thiocyanate
(3)
Following the same procedure using 250 mg (0.47
mmol) of [(3-MeC6H4)3P]AuCl and 92 mg (0.94 mmol)

D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ
/187
185
1
of KSCN; Yield, 212 mg (81%); m.p. (dec.), 119 8C. H
NMR: dꢀ7.20ꢃ7.45 [m, 12H, C6H4], 2.36 [s, 9H, Me].
13C{1H} NMR: dꢀ
for C19H15AuNPSe (564.24 g molꢂ1): C, 40.5; H, 2.7; N,
2.5. Found: C, 40.9; H, 2.9; N, 2.3%.
/
/
2
/
139.9 [d, J(C,P)ꢀ12.4 Hz, C2],
/
2
4
135.0 [d, J(C,P)ꢀ
Hz, C4], 131.6 [d, 3J(C,P)ꢀ
3J(C,P)ꢀ11.9 Hz, C5], 128.7 [d, 1J(C,P)ꢀ
21.6 [s, Me]. 31P{1H} NMR: dꢀ
37.8 [s, P(m-tol)3]. IR
/
14.5 Hz, C6], 133.3 [d, J(C,P)ꢀ
13.0 Hz, C3], 129.5 [d,
60.2 Hz, C1],
/2.6
4.8. [Tri(2-methylphenyl)phosphine]gold selenocyanate
(7)
/
/
/
/
Following the same procedure using 250 mg (0.47
mmol) [(2-MeC6H4)3P]AuCl and 102 mg (0.70 mmol) of
(KBr): 2120 cmꢂ1, s, 2070 cmꢂ1, w, n(CN). MS (FAB):
m/z cations as for 2 with relative intensities 44.0, 21.3,
11.3, and 100%. Elemental analysis: Found: C, 47.0; H,
3.8; N, 2.5; S 5.5% (cf. 2).
1
KSeCN; Yield, 231 mg (81%); m.p. (dec.), 110 8C. H
NMR: dꢀ
/
6.90ꢃ
/
7.52 [m, 12H, C6H4], 2.71 [s, 9H, Me].
143.3 [d, 2J(C,P)ꢀ
13C{1H} NMR: dꢀ
/
/
12.3 Hz, C2],
3
2
134.1 [d, J(C,P)ꢀ
/
9.2 Hz, C6], 132.8 [d, J(C,P)ꢀ
/
8.5
3
4.5. (Dimethylphenylphosphine)gold thiocyanate (4)
Hz, C5], 132.5 [s, C4], 127.3 [d, J(C,P)ꢀ
/
10.0 Hz, C3],
1
3
125.6 [d, J(C,P)ꢀ
Hz, Me]. 31P{1H} NMR: dꢀ
(KBr): 2127 cmꢂ1, s, n(CN). MS (FAB): m/zꢀ
/
59.9 Hz, C1], 23.5 [d, J(C,P)ꢀ
/
7.8
Following the same procedure using 400 mg (1.08
mmol) of (Me2PhP)AuCl and 212 mg (2.16 mmol)
/
15.6 [s, P(o-tol)3]. IR
805
1]ꢁ, 501
/
1
(26.0%) {[(o-tol)3P]2Au}ꢁ, 608 (36.3) [Mꢁ
/
KSCN; Yield, 314 mg (75%); m.p. (dec.), 135 8C. H
2
(100) {[(o-tol)3P]Au}ꢁ. Anal. Calc. for C22H21AuNPSe
(606.32 g molꢂ1): C, 43.6; H, 3.5; N, 2.3. Found: C,
42.9; H, 3.6; N, 2.2%.
NMR: dꢀ
/
7.53ꢃ
/
7.73 [m, 5H, Ph], 1.91 [d, J(H,P)ꢀ
/
10.8 Hz, 6H, Me]. 13C{1H} NMR: dꢀ
132.6 [d,
/
4J(C,P)ꢀ
6], 129.8 [d, J(C,P)ꢀ
15.8 [d, 1J(C,P)ꢀ
/
2.3 Hz, C4], 132.2 [d, J(C,P)ꢀ
/
13.8 Hz, C2/
2
3
/
11.5 Hz, C3/5], C1 not detected,
/
37.7 Hz, Me]. 31P{1H} NMR: dꢀ
/
9.8
[s, PMe2Ph]. IR (KBr): 2112 cmꢂ1, s, 2053 cmꢂ1, w,
n(CN). MS (FAB): m/zꢀ728 (18.4%) {[(Me2PhP)-
Au]2SCN}ꢁ, 473 (7.9) [(Me2PhP)2Au]ꢁ, 394 (74.6)
4.9. (Dimethylphenylphosphine)gold selenocyanate (8)
/
Following the same procedure using 200 mg (0.54
mmol) of (Me2PhP)AuCl and 117 mg (0.81 mmol) of
KSeCN; Yield, 181 mg (76%). The solid product and its
[Mꢁ
1]ꢁ, 335 (100) [(Me2PhP)Au]ꢁ. Anal. Calc. for
/
C9H11AuNPS (393.20 g molꢂ1): C, 27.5; H, 2.8; N, 3.6;
S, 8.2. Found: C, 27.4; H, 2.8; N, 3.6; S 8.0%.
1
solutions decompose at room temperature. H NMR:
2
dꢀ
/
7.51ꢃ
/
7.95 [m, 5H, Ph], 1.87 [d, J(H,P)ꢀ
/
10.6 Hz,
2.4
13.5 Hz, C2/6], 129.7 [d,
11.4 Hz, C3/5], C1 not detected, 15.8 [d,
36.8 Hz, Me]. 31P{1H} NMR: dꢀ
11.0 [s,
PMe2Ph]. IR (KBr): 2114 cmꢂ1, s, n(CN). MS (FAB):
m/zꢀ
776 (5.1%) {[(Me2PhP)Au]2SeCN}ꢁ, 553 (40.2)
[(Me2PhPSe)Au]ꢁ, 473 (17.5) [(Me2PhP)2Au]ꢁ, 442
6H, Me]. 13C{1H} NMR: dꢀ
/
132.1 [d, 4J(C,P)ꢀ
/
4.6. [Tri(ipropyl)phosphine]gold thiocyanate (5)
2
Hz, C4], 132.0 [d, J(C,P)ꢀ
3J(C,P)ꢀ
1J(C,P)ꢀ
/
/
Following the same procedure using 200 mg (0.51
mmol) of [(iPro)3P]AuCl and 100 mg (1.02 mmol) of
/
/
1
KSCN; Yield, 165 mg (78%); m.p., 73 8C. H NMR:
2.35 [sept, 3J(H,H)ꢀ
/
7.4 Hz, 1H, CH], 1.34 [d,
/
dꢀ
3J(H,H)ꢀ
2J(C,P)ꢀ29.2 Hz, CH], 20.6 [s, Me]. 31P{1H} NMR:
dꢀ
69.6 [s, P(iPro)3]. IR (KBr): 2125 cmꢂ1, s, 2075
cmꢂ1, w, n(CN). MS (FAB): m/zꢀ
772 (56.7%)
1]ꢁ, 357 (100)
/
/
7.4 Hz, 6H, Me]. 13C{1H} NMR: dꢀ
/
24.3 [d,
(16.2) [Mꢁ
1]ꢁ, 335 (100) [(Me2PhP)Au]ꢁ. Anal. Calc.
/
/
for C9H11AuNPSe (440.10 g molꢂ1): C, 24.6; H, 2.5; N,
3.2. Found: C, 25.4; H, 2.8; N, 2.9%.
/
/
{[(iPro)3PAu]2SCN}ꢁ, 416 (9.1) [Mꢁ
/
{[(iPro)3P]Au}ꢁ. Anal. Calc. for C10H21AuNPS (415.29
g molꢂ1): C, 28.9; H, 5.1; N, 3.4; S, 7.7. Found: C, 28.8;
H, 5.1; N, 3.4; S, 7.6%.
4.10. (m-Thiocyanato)-bis[(triphenylphosphine)gold]
tetrafluoroborate (9) and hexafluoroantimonate (10),
and (m-selenocyanato)-bis[(triphenylphosphine)gold]
hexafluoroantimonate (15)
4.7. (Triphenylphosphine)gold selenocyanate (6)
100 mg (0.20 mmol) of (Ph3P)AuCl is treated with 43
Following the same procedure using 300 mg (0.60
mmol) of (Ph3P)AuCl and 130 mg (0.90 mmol) of
KSeCN; Yield, 254 mg (75%). The solid product and
its solutions decompose slowly at room temperature. 1H
mg (0.22 mol) of AgBF4 in CH2Cl2 (15 ml) at ꢂ78 8C
/
for 30 min. The cold solution is filtered and added to a
solution of 103 mg (0.20 mmol) of (Ph3P)AuSCN in 10
ml of the same solvent. The reaction mixture is protected
NMR: dꢀ
/
7.53ꢃ
[d, J(C,P)ꢀ13.5 Hz, C2/6], 132.5 [s, C4], 129.3 [s, C3/
5], C1 not detected. 31P{1H} NMR: dꢀ
38.8 [s, PPh3].
IR (KBr): 2120 cmꢂ1, s, n(CN). MS (FAB): m/zꢀ
1024
(2.0%) {[(Ph3P)Au]2SeCN}ꢁ, 721 (8.3) [(Ph3P)2Au]ꢁ,
566 (12.4) [Mꢁ
1]ꢁ, 459 (100) [(Ph3P)Au]ꢁ. Anal. Calc.
/
7.59 [m, Ph]. 13C{1H} NMR: dꢀ
/
134.6
against light and stirred for 3 h at ꢂ78 8C. Subse-
/
2
/
quently, the solvent is evaporated in a vacuum to a
volume of approximately 3 ml and cold pentane is added
/
/
(25 ml) at ꢂ
filtered and dried in a vacuum. Yield, 138 mg (65%);
slow dec. above ꢂ10 8C.
/
30 8C to precipitate the product (9), which is
/
/

186
D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ187
/
The same reaction with 76 mg (0.22 mmol) of AgSbF6
n(CN); 655 cmꢂ1, vs, n(SbF). MS (FAB): m/zꢀ
1061
/
gives 10 in a yield of 177 mg (73%). This product is
unstable above 20 8C.
The same reaction with (Ph3P)AuSeCN (112 mg, 0.20
(100%) {[(m-tol)3PAu]2SCN}ꢁ, 805 (34.5) {[(m-
tol)3P]2Au}ꢁ, 501 (60.7) [(m-tol)3PAu]ꢁ. Anal. Calc.
for C43H42Au2F6NP2SSb (1296.50 g molꢂ1): C, 39.8; H,
3.3; N, 1.1. Found: C, 40.5; H, 3.4; N, 1.1%.
mmol) gives a very unstable product 15 which decom-
poses slowly at ꢂ30 8C. The yield was not determined
/
and no elemental analysis could be obtained.
The solution NMR spectra of 9 and 10 (in CD2Cl2)
are very similar and only the complete data for 10 are
4.12. (m-Thiocyanato)-bis[(dimethylphenylphosphine)-
gold] hexafluoroantimonate (13)
given. 1H NMR: dꢀ
dꢀ
133.8 [d, 2J(C,P)ꢀ
4J(C,P)ꢀ
2.6 Hz, C4], 129.3 [d, J(C,P)ꢀ
5], 126.8 [d, 1J(C,P)ꢀ64.3 Hz, C1]. 31P{1H} NMR
(ꢂ50 8C): dꢀ 1.08 [s,
34.2 [s, PPh3]. 9: 11B NMR: dꢀ
BF4]. 15: 31P{1H} NMR: dꢀ
35.4 [s, PPh3]. IR (KBr) 9:
/
7.46ꢃ
/
7.73 [m, Ph]. 13C{1H} NMR:
Following the procedure given for 10 using (Me2Ph-
P)AuCl (100 mg, 0.27 mmol), (Me2PhP)AuSCN (106
mg, 0.27 mmol) and AgSbF6 (120 mg, 0.35 mmol);
Yield, 199 mg (76%), decomposes slowly at room
/
/
13.5 Hz, C2/6], 132.4 [d,
3
/
/12.5 Hz, C3/
/
/
/
/
ꢂ
/
temperature. 1H NMR: dꢀ
1.51 [s, 6H, Me]. 13C{1H} NMR: dꢀ
2J(C,P)ꢀ13.1 Hz, C2/6], 132.7 [d, 4J(C,P)ꢀ
C4], 130.7 [d, 1J(C,P)ꢀ
63.0 Hz, C1], 129.9 [d,
3J(C,P)ꢀ12.3 Hz, C3/5], 15.5 [d, 1J(C,P)ꢀ
40.7 Hz,
5.38 [s, PMe2Ph]. IR
/
7.53ꢃ
/
7.73 [m, 5H, Ph],
134.0 [d,
2.3 Hz,
/
2155 cmꢂ1, s, 2122 cmꢂ1, w, 2070 cmꢂ1, vw, n(CN);
1053 cmꢂ1, vs, n(BF). 10: 2154 cmꢂ1, s, 2133 cmꢂ1, w,
2080 cmꢂ1, vw, n(CN); 656 cmꢂ1, vs, n(SbF). 15: 2155
cmꢂ1, s, 2122 cmꢂ1, w, n(CN); 648 cmꢂ1, vs, n(SbF).
/
/
/
/
/
/
Me]. 31P{1H} NMR (ꢂ
/
50 8C): dꢀ
/
MS
(FAB)
9/10:
m/zꢀ
/
977
(43.9/54.2%)
(KBr): 2120 cmꢂ1, s, 2070 cmꢂ1, vw, n(CN); 655 cmꢂ1
vs, n(SbF).
,
{[(Ph3P)Au]2SCN}ꢁ, 459 (100) [(Ph3P)Au]ꢁ.
Anal. Calc. for C37H30Au2BF4NP2S (9) (1063.40 g
molꢂ1): C, 41.8; H, 2.8; N, 1.3. Found: C, 43.6; H, 3.2;
N, 1.1%. Anal. Calc. for C37H30Au2F6NP2SSb (10)
(1212.34 g molꢂ1): C, 36.7; H, 2.5; N, 1.1. Found: C,
37.2; H, 2.6; N, 1.0%.
4.13. (m-Thiocyanato)-bis{[tri(ipropyl)phosphine]gold}
hexafluoroantimonate (14)
Following the procedure given for 10 using
[(iPro)3P]AuCl (67 mg, 0.17 mmol), [(iPro)3P]AuSCN
(70 mg, 0.17 mmol) and AgSbF6 (86 mg, 0.22 mmol);
Yield, 107 mg (63%), decomposes slowly at room
4.11. (m-Thiocyanato)-bis{[tri(2- and 3-methylphenyl)-
phosphine]gold} hexafluoroantimonate (11) and (12)
temperature. 1H NMR: dꢀ
/
2.33 [sept, 3J(H,H)ꢀ
7.2 Hz, 6H, Me].
69.6 [s, P(iPro)3]. IR
/7.2
Following the procedure given for 10 using [(2-/3-
MeC6H4)3P]AuCl (96 mg, 0.18 mmol), AgSbF6 (80 mg,
0.23 mmol) and [(2-/3-MeC6H4)3P]AuSCN (100 mg,
0.18 mmol) gave yields of 196/201 mg (84/86%) for 11/
12. Both compounds decompose slowly at ambient
Hz, 1H, CH], 1.32 [d, 3J(H,H)ꢀ
/
31P{1H} NMR (ꢂ
/
50 8C): dꢀ
/
(KBr): 2155 cmꢂ1, s, 2127 cmꢂ1, w, n(CN); 656
cmꢂ1, vs, n(SbF).
temperature.
1
11: H NMR: dꢀ
/
6.93ꢃ7.59 [m, 24H, C6H4], 2.64 [s,
/
18H, Me]; 13C{1H} NMR: dꢀ
/
143.3 [d, J(C,P)ꢀ
/
12.8
8.5 Hz, C6], 133.0 [d,
4.14. Crystal structure determination
2
Hz, C2], 134.2 [d, 2J(C,P)ꢀ
/
3J(C,P)ꢀ
3J(C,P)ꢀ
3J(C,P)ꢀ
/
7.3 Hz, C5], 132.9 [s, C4], 127.3 [d,
10.0 Hz, C3], C1 not detected, 23.4 [d,
The crystalline samples were placed in inert oil,
mounted on a glass pin, and transferred to the cold
gas stream of the diffractometer. Crystal data were
/
/
12.3 Hz, Me]; 31P{1H} NMR (ꢂ
/
50 8C): dꢀ
/
9.2 [s, P(o-tol)3]. IR (KBr): 2158 cmꢂ1, s, 2124 cmꢂ1, w,
2075 cmꢂ1, vw, n(CN); 656 cmꢂ1, vs, n(SbF). MS
collected using a Nonius DIP2020 system with mono-
˚
0.71073 A) radiation at
chromated Mo Ka (lꢀ
/
(FAB): m/zꢀ
/
1061 (95.2%) {[(o-tol)3PAu]2SCN}ꢁ, 805
ꢂ
(
/
130 8C. The structures were solved by direct methods
SHELXS-97) and refined by full-matrix least-squares
calculations on F2
SHELXL-97). Non-hydrogen atoms
(18.1) {[(o-tol)3P]2Au}ꢁ, 501 (100) [(o-tol)3PAu]ꢁ.
Anal. Calc. for C43H42Au2F6NP2SSb (1296.50
g
(
molꢂ1): C, 39.8; H, 3.3; N, 1.1. Found: C, 41.8; H,
3.5; N, 1.0%.
were refined with anisotropic displacement parameters.
Hydrogen atoms were located and included into the
refinement with isotropic contributions (2) or were
placed in idealized positions and refined using a riding
model with fixed isotropic contributions (1, 4, 5 and 7),
respectively. Further information on crystal data, data
collection and structure refinement are summarized in
Table 2. Important interatomic distances and angles are
shown in the corresponding figure captions.
1
12: H NMR: dꢀ
/
7.20ꢃ7.45 [m, 24H, C6H4], 2.35 [s,
/
18H, Me]. 13C{1H} NMR: dꢀ
/
140.3 [d, J(C,P)ꢀ12.3
/
2
Hz, C2], 135.0 [d, 2J(C,P)ꢀ
/
14.6 Hz, C6], 133.8 [d,
4J(C,P)ꢀ
/
2.1 Hz, C4], 131.6 [d, J(C,P)ꢀ
/
13.1 Hz, C3],
12.5 Hz, C5], C1 not detected, 21.6
[s, Me]. 31P{1H} NMR (ꢂ
50 8C): dꢀ34.0 [s, P(m-tol)3].
IR (KBr): 2154 cmꢂ1, s, 2122 cmꢂ1, w, 2075 cmꢂ1, vw,
3
3
129.8 [d, J(C,P)ꢀ
/
/
/

D. Schneider et al. / Inorganica Chimica Acta 352 (2003) 179ꢃ
/187
187
[10] A.R. Al-Arfaj, A.A. Saeed, M.N. Akhtar, A.A. Isab, J. Coord.
Chem. 43 (1998) 257.
5. Supplementary material
[11] T. Mathieson, A. Schier, H. Schmidbaur, J. Chem. Soc., Dalton
Trans. (2001) 1196.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
[12] M.N. Akhtar, A.A. Isab, A.R. Al-Arfaj, M.S. Hussain, Polyhe-
dron 16 (1997) 125.
Data Centre, CCDC No. 192917ꢃ192921 for com-
/
[13] J.L. Burmeister, J.B. Melpolder, J. Chem. Soc., Chem. Commun.
(1973) 613.
pounds 1, 2, 4, 5, 7. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
[14] J.L. Burmeister, J.B. Melpolder, Inorg. Chim. Acta 49 (1981)
115.
Union Road, Cambridge, CB2 1EZ, UK (fax: ꢁ44-
/
1233-336-033; e-mail deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
[15] M.M. El-Etri, W.M. Scovell, Inorg. Chem. 29 (1990) 480.
[16] N.J. DeStefano, J.L. Burmeister, Inorg. Chem. 10 (1971)
998.
[17] F. Cariati, D. Galizzioli, L. Naldini, Chim. Ind. (Milan) 52 (1970)
995.
Acknowledgements
[18] R. Uson, P. Royo, A. Laguna, J. Garcia, Rev. Acad. Cienc.
Zaragoza 28 (1973) 67.
This work was generously supported by Fonds der
Chemischen Industrie, Deutsche Forschungsge-
meinschaft and Volkswagenstiftung. Donation of chem-
icals by Degussa AG and Heraeus GmbH is gratefully
acknowledged.
[19] P.G. Jones, A.G. Maddock, M.J. Mays, M.J. Muir, A.F.
Williams, J. Chem. Soc., Dalton Trans. (1977) 1434.
[20] P.F. Barron, L.M. Engelhardt, P.C. Healy, J. Oddy, A.H. White,
Aust. J. Chem. 40 (1987) 1545.
[21] G.C.H. Jones, P.G. Jones, A.G. Maddock, M.J. Mays, P.A.
Vergnano, A.F. Williams, J. Chem. Soc., Dalton Trans. (1977)
1440.
[22] R. Uson, A. Laguna, M.V. Castillo, Synth. React. Inorg. Met.
Org. Chem. 9 (1979) 317.
References
[23] P.M.T.M. Van Attekum, J.W.A. Van der Velden, J.M. Trooster,
Inorg. Chem. 19 (1980), 19, 701.
[1] H.G. Raubenheimer, S. Cronje, in: H. Schmidbaur (Ed.), Gold,
Progress in Chemistry, Biochemistry and Technology, Wiley,
Chichester, 1999, p. 557.
[24] C.A. McAuliffe, R.V.D. Parish, P.D. Randall, J. Chem. Soc.,
Dalton Trans. (1979) 1730.
[25] M.A. Bennett, D.C.R. Hockless, A.D. Rae, L.L. Welling, A.C.
Willis, Organometallics 20 (2001) 79.
[2] M.D. Adams, M.W. Jones, D.W. Dew, in: H. Schmidbaur (Ed.),
Gold, Progress in Chemistry, Biochemistry and Technology,
Wiley, Chichester, 1999, p. 65.
[26] A.J. Carty, A. Efraty, Inorg. Chem. 8 (1969) 543.
[27] M. Bardaj´ı, A. Laguna, Inorg. Chim. Acta 318 (2001) 38.
[28] H. Schmidbaur, A. Hamel, N.W. Mitzel, A. Schier, S. Nogai,
Proc. Natl. Acad. Sci. USA 99 (2002) 4919.
[29] A. Bayler, A. Bauer, H. Schmidbaur, Chem. Ber. 130 (1997)
115.
[3] H. Grossmann, K.E. Saenger, E. Vinaricky, in: H. Schmidbaur
(Ed.), Gold, Progress in Chemistry, Biochemistry and Technol-
ogy, Wiley, Chichester, 1999, p. 199.
[4] R.J. Puddephatt, in: H. Schmidbaur (Ed.), Gold, Progress in
Chemistry, Biochemistry and Technology, Wiley, Chichester,
1999, p. 237.
[30] P.G. Jones, G.M. Sheldrick, R. Uson, A. Laguna, Acta Crystal-
logr. B 36 (1980) 1486.
[5] (a) Gmelin Handbook of Inorganic Chemistry, Gold, Supplement
Volume B1, Springer, Berlin, 1992;
[31] M. Polak, M. Gruebele, R.J. Saykally, J. Chem. Phys. 87 (1987)
3352.
(b) Gmelin Handbook of Inorganic Chemistry, Gold, Supplement
Volume B2, Springer, Berlin, 1994.
[32] N.C. Baenziger, W.E. Bennett, D.M. Soboroff, Acta Crystallogr.
B 32 (1976) 962.
˚
[33] S. Ahrland, K. Dreisch, B. Nore´n, A. Oskarsson, Mater. Chem.
[6] M.D. Adams, M.W. Jones, D.W. Dew, in: H. Schmidbaur (Ed.),
Gold, Progress in Chemistry, Biochemistry and Technology,
Wiley, Chichester, 1999, p. 82.
Phys. 35 (1993) 281.
[34] D.V. Toronto, B. Weissbart, D.S. Tinti, A.L. Balch, Inorg. Chem.
35 (1996) 2482.
[35] H. Schmidbaur, B. Brachthauser, O. Steigelmann, H. Beruda,
¨
[7] C.K. Mirabelli, R.K. Johnson, D.T. Hill, J. Med. Chem. 29 (1986)
218.
[8] C.F. Shaw, III, in: H. Schmidbaur (Ed.), Gold, Progress in
Chemistry, Biochemistry and Technology, Wiley, Chichester,
1999, p. 259.
Chem. Ber. 125 (1992) 2705.
[36] A.K. Al-Saa´dy, C.A. McAuliffe, R.V. Parish, J.A. Sandbank,
Inorg. Synth. 23 (1985) 191.
[9] C.F. Shaw, III, in: H. Schmidbaur (Ed.), Gold, Progress in
Chemistry, Biochemistry and Technology, Wiley, Chichester,
1999, p. 289.
[37] C.S.W. Harker, E.R.T. Tiekink, Acta Crystallogr. C 47 (1991)
878.