Synthesis and reactivity of the ligand 1,2-bis(pyridine-2-ylthio)-1,2-dicarba-closo-dodecaborane. Crystal structure of [Ag{1,2-(C5H4NS)2-1,2-C2B 10H10}(PPh3)]OTf

Article abstract of DOI:10.1016/S0022-328X(98)00501-4

A new o-carborane disubstituted ligand containing pyridinethiolate groups, 1,2-(C₅H₄NS)₂-1,2-C₂B ₁₀H₁₀, has been synthesised and its reactivity toward silver and gold studied. Thus, the reaction of AgOTf (OTf=trifluoromethanesulfonate) with 1,2-(C₅H₄NS)₂-1,2-C₂B ₁₀H₁₀ in the molar ratio 1:1 or 1:2 affords the cationic three-coordinate silver(I) derivative [Ag(OTf){1,2-(C₅H₄NS)₂-1,2-C₂B ₁₀H₁₀}] or the four-coordinate one [Ag{1,2-(C₅H₄NS)₂-1,2-C₂B ₁₀H₁₀}₂]OTf, respectively. Other three-coordinate silver(I) complexes of stoichiometry [Ag{1,2-(C₅H₄NS)₂-1,2-C₂B ₁₀H₁₀}L] OTf (L=tertiary phosphines or triphenylarsine) have been synthesised by reaction of [Ag(OTf)L] with the carborane derivative. The complex [Au₂(PPh₃)₂{1,2-(C₅H ₄NS)₂-1,2-C₂B₁₀H ₁₀}](OTf)₂ has also been prepared by reaction of the ligand with [Au(OTf)(PPh₃)] (molar ratio 1:2). The crystal structure of [Ag{1,2-(C₅H₄NS)₂-1,2-C₂B ₁₀H₁₀}(PPh₃)]OTf has been established by X-ray diffraction studies.

Full text of DOI:10.1016/S0022-328X(98)00501-4

Journal of Organometallic Chemistry 561 (1998) 13–18
Synthesis and reactivity of the ligand
1,2-bis(pyridine-2-ylthio)-1,2-dicarba-closo-dodecaborane. Crystal
structure of [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}(PPh3)]OTf
Olga Crespo, M. Concepcio´n Gimeno, Antonio Laguna *
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received 22 August 1997; received in revised form 11 February 1998
Abstract
A new o-carborane disubstituted ligand containing pyridinethiolate groups, 1,2-(C5H4NS)2-1,2-C2B10H10, has been synthesised
and its reactivity toward silver and gold studied. Thus, the reaction of AgOTf (OTf=trifluoromethanesulfonate) with 1,2-
(C5H4NS)2-1,2-C2B10H10 in the molar ratio 1:1 or 1:2 affords the cationic three-coordinate silver(I) derivative [Ag(OTf){1,2-
(C5H4NS)2-1,2-C2B10H10}] or the four-coordinate one [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}2]OTf, respectively. Other
three-coordinate silver(I) complexes of stoichiometry [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}L] OTf (L=tertiary phosphines or
triphenylarsine) have been synthesised by reaction of [Ag(OTf)L] with the carborane derivative. The complex [Au2(PPh3)2{1,2-
(C5H4NS)2-1,2-C2B10H10}](OTf)2 has also been prepared by reaction of the ligand with [Au(OTf)(PPh3)] (molar ratio 1:2). The
crystal structure of [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}(PPh3)]OTf has been established by X-ray diffraction studies. © 1998
Elsevier Science S.A. All rights reserved.
Keywords: Silver(I); Gold(I); o-Carborane; Pyridinethiolate
1. Introduction
C2B10H10}2(1,2-S2-1,2-C2B10H10)2] [5], in which two of
the gold atoms exhibit an unusual tetrahedral geometry
whereas the other two present linear geometries, or the
silver derivative [Ag4(v3-1-S-1,2-C2B10H11)2(OTf)2-
(PPh3)4], which presents an unprecedented structure in
the chemistry of silver thiolates [6]. Furthermore, par-
tially degraded o-carborane derivatives have provided
interesting structures. Partially degraded thioether
derivatives have been used for the modulation in hy-
dride–ruthenium bonds [7], whereas in gold chemistry
the partially degraded diphosphine [7,8-(PPh2)2-7,8-
C2B9H10]− has been used in the synthesis of the cluster
[Au4{7,8-(PPh2)2-7,8-C2B9H10}2-(AsPh3)2] [8].
The chemistry concerned with o-carborane deriva-
tives has been widely studied because of their potential
applications [1]. These result from their high boron
content (preparation of tumour-seeking drugs for
boron neutron capture therapy [2]) or as a consequence
of the specific properties of carborane clusters as their
remarkable thermal and chemical stability, which make
then suitable for the synthesis of polymers for high
temperature [3], neutron shielding purposes ([1]b) or for
firing to form ceramics related to boron carbide [4].
Other properties of the carborane, such as their rigid
backbones, have allowed the synthesis of complexes
that exhibit novel structures. Some examples of this
behaviour are the gold complex [Au4{1,2-(PPh2)2-1,2-
This facts prompt us in the preparation of different
ligands of o-carborane in order to study their reactivity,
as well as the possible formation of unusual structures.
Here we report on the synthesis of a new ligand that
has two pyridinethiolate groups attached to the carbon
* Corresponding author. Tel.: +34 976 761185; fax: +34 976
761187; e-mail: alaguna@posta.unizar.es
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00501-4

14
O. Crespo et al. / Journal of Organometallic Chemistry 561 (1998) 13–18
the spectrum displays only three resonances as two of
them are overlapped. One of the signals consists of two
doublets; whereas the other two are broad multiplets.
The molecular peak [M]+ [m/z=363 (100%)] is
present in the positive ion liquid secondary ion mass
spectrum (LSIMS) of this ligand with coincident-calcu-
lated and experimental isotopic distributions.
Scheme 1. (i) 2 LinBu, (ii) 2 C10H8N2S2.
atoms of the o-carborane, 1,2-(C5H4NS)2-1,2-C2B10H10,
2.2. Reacti6ity of 1,2-(C5H4NS)2-1,2-C2B10H10
and the first results of its reactivity.
We have studied the reactivity of 1,2-(C5H4NS)2-1,2-
C2B10H10 (1) with silver and gold complexes. The coor-
dination of the ligand to the metallic centre takes place
through the nitrogen atom, as is evidenced by the
crystal structure of one of the complexes. Thus, the
treatment of 1 with AgOTf (OTf=trifluoromethane-
sulfonate) in molar ratios 1:1 or 1:2 affords the three-
2. Results and discussion
2.1. Synthesis of the ligand 1,2-(C5H4NS)2-1,2-
C2B10H10
We have synthesised the new carborane derivative by
addition of C10H8N2S2 (2,2%-dithiopyridine) to a solu-
tion of 1,2-Li2-1,2-C2B10H10 in diethyl ether in the
molar ratio 2:1. After work up, the new ligand 1,2-
(C5H4NS)2-1,2-C2B10H10 (1) can be isolated in high
yield (Scheme 1).
coordinate
complex
[Ag(OTf){1,2-(C5H4NS)2-1,2-
C2B10-H10}] (2) or the four-coordinate one
[Ag{1,2-(C5H4NS)2-1,2-C2B10H10}2]OTf (3), respectively
(Scheme 2).
Acetone solutions of complexes 2 and 3 behave as 1:1
electrolytes. In the case of compound 2 this is due to
the lability of the OTf ligand. The solid IR spectra of
these derivatives present the w(BH) absorptions at 2615
(2) and 2579 (3) cm−1, respectively; those correspond-
ing to the w(CN) vibration appear at 1583 (2) and 1578
(3) cm−1, whereas those assigned to the OTf ligand [11]
are different for both compounds. For complex 3, the
Compound 1 is a moisture- and air-stable pale yellow
solid. It behaves as non-conductor in acetone solutions.
In its IR spectrum, the BꢀH stretching modes [9] ap-
pear as a broad absorption centred at 2618 cm−1 and
those due to w(CN) [10] at 1574 cm−1
.
1
The H-NMR spectrum of 1 shows the equivalence
of the two pyridinethiolate groups. Although four sig-
nals are expected for the four different hydrogen atoms,
bands correspond to
a
non-coordinated anion
[was(SO3)=1268, ws(CF3)=1224,
was(CF3)=1151,
Scheme 2. (i) AgOTf, (ii) 1/2 AgOTf, (iii) [Ag(OTf)L], (iv) 2 [Au(OTf)(PPh3)].

O. Crespo et al. / Journal of Organometallic Chemistry 561 (1998) 13–18
15
Fig. 1. Structure of the cation of complex 4 in the crystal with the atom numbering scheme. H atoms are omitted for clarity; radii are arbitrary.
ws(SO3) 1032 cm−1], whereas for complex 2, they corre-
spond to a covalent anion [was(SO3)=1272 and 1243,
ws(CF3)=1224, was(CF3)=1178, ws(SO3) 1028 cm−1].
tions corresponding to the w(BH) frequencies, as well as
those assigned to the w(CN) vibrations at 2614 and
1583 cm−1, respectively.
The 31P{1H}-NMR spectrum shows a broad singlet
1
In their H-NMR spectra, the resonances observed
1
for the hydrogen atoms of the pyridinethiolate groups
appear displaced upfield compared with the free ligand.
The spectrum of 2 consist of four signals, but in the
case of complex 3 only three resonances appear.
In the LSIMS+ mass spectra of both complexes, the
most intense peak corresponds to the fragment
[Ag{(C5H4NS)2C2B10H10}]+ [m/z=470]. For complex
3 the peak assigned to [M–OTf]+ [m/z=833 (3%)] is
also present.
Displacement of the OTf anion in silver complexes
[Ag(OTf)L] by 1 affords the three-coordinate complexes
[Ag{1,2-(C5H4NS)2-1,2-C2B10H10}L]OTf [L=PPh3 (4),
PPh2Me (5), AsPh3 (6)].
for the two phosphorus atoms. In the H-NMR spec-
trum, the hydrogen atoms of the phenyl, carborane
(BH) and pyridinethiolate groups appear as broad
resonances.
In the LSIMS+ mass spectrum, the peak [M–
2OTf]+ does not appear but that corresponding to
[Au{(C5H4NS)2C2B10H10}(PPh3)]+ is present [m/z=
822 (28%)]; although the most intense peaks are those
assigned to [Au(PPh3)]+ and [Au(PPh3)2]+ (m/z=459
(100%) and 721 (87%)), respectively.
2.3. Crystal structure determination of complex 4
The 31P{1H}-NMR spectra of complexes 4 and 5
display a broad resonance. When the spectra were
recorded at −55°C, the signal splits into two doublets
that correspond to the coupling of the phosphine phos-
phorus with the silver nuclei 107Ag and 109Ag. The
1H-NMR spectra of these complexes exhibit broad
signals for the pyridinethiolate and phenyl protons. In
the spectrum of complex 5 a doublet is present that is
assigned to the methyl protons of the phosphine.
The LSIMS+ mass spectra of 4–6 exhibit m/z=732
(27%, 4), 671 (20%, 5) and 777 (4%, 6) for the cation
molecular peaks, [Ag{(C5H4NS)2C2B10H10}L]+; al-
though, those corresponding to [AgL]+ are the most
intense ones.
The molecular structure of the cation of complex 4 is
shown in Fig. 1. Selected bond lengths and angles are
presented in Table 1 and atomic coordinates in Table 2.
It contains a silver atom bonded to one phosphorus
and to two nitrogen atoms, corresponding to the
triphenylphosphine and carborane derivative, respec-
tively. There are not many examples of silver deriva-
tives with this type of coordination, as far as we are
aware only the complexes [IrAg(p5-C5Me5)(pz)3(PPh3)]
[12] and [Ag{P(C6H4Me-4)3}{BPh2(pz)2}] [13] (pz=
pyrazolyl) have been reported; although the latter has a
pseudo-three-coordination for the silver atom. The ge-
ometry for complex 4 is distorted from the trigonal
planar, mainly because the restricted bite angle of the
carborane ligand, N(1)–Ag–N(2)=84.26(8)°. Conse-
quently, the others are wider than the ideal 120°, N(1)–
Ag–P=134.10(6)° and N(2)–Ag–P=136.43(6)°. The
The reaction of [Au(OTf)(PPh3)] and 1,2-(C5H4NS)2-
1,2-C2B10H10 in molar ratio 2:1 affords the complex
[Au2{1,2-(C5H4NS)2-1,2-C2B10H10}(PPh3)2](OTf)2 (7).
The IR spectrum of this product displays the absorp-
˚
silver atom lies 0.29 A out of the plane formed by the

16
O. Crespo et al. / Journal of Organometallic Chemistry 561 (1998) 13–18
Table 2
P, N(1) and N(2) atoms. The AgꢀN distances, 2.345(2)
Atomic coordinates (×104) and equivalent isotropic displacement
˚
and 2.350(2) A, are longer to those found in the com-
2
3
˚
parameters (A ×10 ) for 4
plex [IrAg(p5-C5Me5)(pz)3(PPh3)] (2.211(4) and 2.205(3)
˚
A) [12] or the heterotetranuclear derivative [Au2Ag2{v-
x
y
z
Ueq
˚
(PPh2)2N}2(OClO3)2(PPh3)2] (2.239(4) A) [14], which
Ag
P
S(1)
S(2)
2451(1)
3791(1)
1982(1)
2975(1)
1083(2)
1994(2)
1844(2)
2359(2)
1005(2)
243(2)
−484(2)
−421(2)
372(2)
2263(2)
2053(2)
1467(2)
1151(2)
1443(2)
1253(2)
959(2)
2424(1)
2560(1)
557(1)
6482(1)
7304(1)
7302(1)
5464(1)
6746(1)
5098(1)
6589(2)
5635(2)
7113(2)
7391(2)
7230(2)
6827(2)
6608(2)
4771(2)
3958(2)
3471(2)
3798(2)
4608(2)
5637(2)
6430(2)
5374(2)
4897(2)
6955(2)
6195(2)
5259(2)
5428(2)
6470(2)
6233(2)
6711(2)
5878(2)
5422(2)
5794(2)
6618(2)
7079(2)
7898(2)
8613(2)
9001(2)
8685(2)
7977(2)
7586(2)
8066(2)
7934(2)
8480(2)
9153(2)
9282(2)
8743(1)
6206(2)
6744(2)
6406(2)
5995(1)
5218(3)
5262(2)
4625(1)
4977(2)
25(1)
21(1)
28(1)
25(1)
23(1)
22(1)
22(1)
21(1)
26(1)
34(1)
39(1)
37(1)
32(1)
22(1)
28(1)
33(1)
30(1)
27(1)
22(1)
26(1)
26(1)
24(1)
30(1)
30(1)
29(1)
26(1)
27(1)
31(1)
24(1)
32(1)
39(1)
38(1)
36(1)
29(1)
21(1)
29(1)
32(1)
30(1)
30(1)
27(1)
22(1)
34(1)
47(1)
40(1)
32(1)
27(1)
42(1)
78(1)
60(1)
45(1)
51(1)
67(1)
72(1)
95(1)
have trigonal silver atoms, but are in between the
values obtained for the complex [Ag{P(C6H4Me-
˚
4)3}{BPh2(pz)2}] (2.194(4) and 2.411(4) A) [13]. How-
690(1)
ever, they are also comparable with those in the
tetrahedral compounds [Ag(dppf)(phen)]ClO4 (2.343(3)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
B(1)
B(2)
B(3)
B(4)
B(5)
B(6)
B(7)
B(8)
B(9)
B(10)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
S(3)
1939(2)
2072(2)
−320(2)
−254(2)
1165(2)
864(2)
1373(2)
2158(2)
2430(2)
1328(2)
1081(2)
1581(2)
2322(2)
2554(2)
−221(2)
−958(2)
−1301(2)
−848(2)
−1350(2)
−2008(2)
−1936(2)
−1245(2)
−843(2)
−1946(2)
2547(2)
2766(2)
2914(2)
2807(2)
2561(2)
2444(2)
3556(2)
3616(2)
4412(2)
5153(2)
5105(2)
4310(2)
1685(2)
935(2)
236(2)
286(2)
1026(2)
˚
and 2.361(3) A) [15] or [Ag{(PPh2)2C2B10-
˚
H10}(phen)]ClO4 (2.312(5) and 2.333(5) A) [16]. The
˚
AgꢀP bond length of 2.3832(7) A is of the same order
5
˚
as that in [IrAg(p -C5Me5)(pz)3(PPh3)] (2.341(1) A) or
the shortest in [Ag(dppf)(PPh3)]ClO4 (2.4244–
˚
2.4802(12) A).
3. Experimental
IR spectra were recorded in the range 4000–200
cm−1 on a Perkin-Elmer 883 spectrophotometer using
919(2)
1791(2)
1941(2)
1354(2)
1858(2)
2762(2)
2798(2)
2503(2)
4729(2)
4606(2)
5298(2)
6126(2)
6262(2)
5569(2)
3987(2)
4554(2)
4716(2)
4310(2)
3746(2)
3591(2)
3913(2)
4359(2)
4340(2)
3857(2)
3397(2)
3426(2)
1517(1)
1960(2)
671(2)
Table 1
˚
Selected bond lengths (A) and angles (°) for complex 4
˚
Bond lengths (A)
AgꢀN(1)
AgꢀP
PꢀC(41)
2.345(2)
2.3832(7)
1.825(3)
1.777(3)
1.780(3)
1.343(4)
1.340(3)
1.813(4)
1.387(4)
1.388(4)
1.384(4)
1.394(4)
AgꢀN(2)
PꢀC(31)
PꢀC(21)
2.350(2)
1.822(3)
1.829(3)
1.793(3)
1.797(3)
1.347(4)
1.348(4)
1.393(4)
1.382(5)
1.379(4)
1.370(4)
S(1)ꢀC(1)
S(2)ꢀC(2)
N(1)ꢀC(3)
N(2)ꢀC(12)
C(1)ꢀC(2)
C(4)ꢀC(5)
C(6)ꢀC(7)
C(9)ꢀC(10)
C(11)ꢀC(12)
S(1)ꢀC(3)
S(2)ꢀC(8)
N(1)ꢀC(7)
N(2)ꢀC(8)
C(3)ꢀC(4)
C(5)ꢀC(6)
C(8)ꢀC(9)
C(10)ꢀC(11)
Bond angles (°)
N(1)ꢀAgꢀN(2)
N(2)ꢀAgꢀP
C(31)ꢀPꢀC(21)
C(31)ꢀPꢀAg
84.26(8)
136.43(6)
100.50(6)
117.67(10)
114.43(9)
103.39(13)
119.1(2)
116.5(2)
119.6(2)
125.9(2)
122.3(2)
126.1(2)
111.9(2)
118.0(2)
115.4(2)
117.6(3)
119.4(3)
123.7(3)
121.6(2)
N(1)ꢀAgꢀP
134.10(6)
105.29(13)
107.97(14)
110.06(9)
103.73(13)
117.7(3)
123.0(2)
123.8(2)
119.0(2)
112.1(2)
118.3(2)
119.2(2)
122.1(2)
123.7(3)
120.8(3)
119.3(3)
122.1(3)
114.7(2)
118.4(3)
C(31)ꢀPꢀC(41)
C(41)ꢀPꢀC(21)
C(41)ꢀPꢀAg
C(21)ꢀPꢀAg
C(1)ꢀS(1)ꢀC(3)
C(3)ꢀN(1)ꢀC(7)
C(7)ꢀN(1)ꢀAg
C(12)ꢀN(2)ꢀAg
B(5)ꢀC(1)ꢀS(1)
B(9)ꢀC(1)ꢀS(1)
S(1)ꢀC(1)ꢀC(2)
B(8)ꢀC(2)ꢀS(2)
B(1)ꢀC(2)ꢀS(2)
N(1)ꢀC(3)ꢀC(4)
C(4)ꢀC(3)ꢀS(1)
C(6)ꢀC(5)ꢀC(4)
N(1)ꢀC(7)ꢀC(6)
N(2)ꢀC(8)ꢀS(2)
C(8)ꢀC(9)ꢀC(10)
C(2)ꢀS(2)ꢀC(8)
C(3)ꢀN(1)ꢀAg
C(12)ꢀN(2)ꢀC(8)
C(8)ꢀN(2)ꢀAg
B(2)ꢀC(1)ꢀS(1)
B(1)ꢀC(1)ꢀS(1)
B(4)ꢀC(2)ꢀS(2)
B(9)ꢀC(2)ꢀS(2)
S(2)ꢀC(2)ꢀC(1)
N(1)ꢀC(3)ꢀS(1)
C(5)ꢀC(4)ꢀC(3)
C(5)ꢀC(6)ꢀC(7)
N(2)ꢀC(8)ꢀC(9)
C(9)ꢀC(8)ꢀS(2)
1720(1)
−5256(2)
−4631(2)
−5474(2)
−6003(2)
−4694(2)
−4018(1)
−5218(2)
−4391(2)
O(1)
O(2)
O(3)
C(100)
F(1)
2026(2)
1339(3)
810(2)
1002(2)
2073(2)
F(2)
F(3)
Ueq is defined as one third of the trace of the orthogonalised Uij tensor.
Nujol mulls between polyethylene sheets. Conductivi-
ties were measured in ca. 5×10−4 mol dm−3 solutions
with a Philips 9509 conductimeter. C and H analyses
C(11)ꢀC(10)ꢀC(9) 119.2(3)
N(2)ꢀC(12)ꢀC(11) 123.3(3)
C(10)ꢀC(11)ꢀC(12) 118.6(3)

O. Crespo et al. / Journal of Organometallic Chemistry 561 (1998) 13–18
17
1
were carried out with a Perkin-Elmer 2400 microana-
lyzer. Mass spectra were recorded on a VG autospec,
with the LSIMS technique, using nitrobenzyl alcohol
as matrix. NMR spectra were recorded on a Varian
Unity 300 spectrometer and a Bruker ARX 300 spec-
trometer in CDCl3. Chemical shifts are cited relative
to SiMe4 (1H, external) and 85% H3PO4 (31P, exter-
nal). o-Carborane (Dexsil Chemical) and C10H8N2S2
(Aldrich) were analytical reagent grade and used as-
given. The starting materials [Ag(OTf)L] were pre-
pared by reaction of Ag(OTf) and the ligand L in
dichloromethane. [Au(OTf)(PPh3)] was obtained from
[AuCl(PPh3)] [17] and Ag(OTf) in dichloromethane.
5.3; S, 15.5. L
M=134 V−1 cm2 mol−1. H-NMR, l:
8.85 (d, 1H), 7.92 (m, br, 2 H), 7.55 (m, br, 1H).
3.4. [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}L]OTf
[L=PPh3 (4), PPh2Me (5), AsPh3 (6)]
To a solution of 1,2-(C5H4NS)2-1,2-C2B10H10 (0.036
g, 0.1 mmol) in dichloromethane (30 cm3), [Ag(OTf)L]
was added (0.1 mmol; 0.052 g, L=PPh3; 0.046 g,
L=PPh2Me; 0.056 g, L=AsPh3). The solution was
stirred for 30 min and concentrated to ca. 5 cm3.
Addition of diethyl ether (10 cm3) gave complexes
4–6 as white solids. 4: yield 65%. Anal. Calc. for
C31H33AgB10F3N2O3PS3: C, 42.2; H, 3.8; N, 3.2; S,
11.0. Found: C, 42.65; H, 3.75; N, 2.65; S, 10.4.
3.1. 1,2-(C5H4NS)2-1,2-C2B10H10 (1)
LM=94 V−1 cm2 mol−1 1H-NMR, l: 9.38 (d, 1H),
.
To a solution of 1,2-C2B10H10 (2.88 g, 20 mmol) in
diethyl ether (100 cm3) at 0°C, and under nitrogen
atmosphere LinBu (8 cm3, 2.5 M) was added. After
stirring for 30 min, C10H8N2S2 (4.40 g, 40 mmol) was
added. The mixture was warmed to r.t. and washed
with water (3×40 cm3). The organic phase was
threated with MgSO4, and after 30 min the MgSO4
was filtered off. Concentration of the solution and
addition of hexane afforded bright yellow crystals of
1. Yield, 75%. Anal. Calc. for C12H18B10N2S2: C,
39.75; H, 5.05; N, 7.7; S, 17.15. Found: C, 39.45; H,
7.92 (t, 1H), 7.70 (t, 1H), 7.76 (d, 1H), 7.3–7.5 (m,
br, 15H). 31P{1H}-NMR, l: 12.9 (2 d, J 109AgP=
712.3, J 107AgP=619.4 Hz). 5: yield 50%. Anal. Calc.
for C26H31AgB10F3N2O3PS3: C, 38.1; H, 3.8; N, 3.4;
S,11.75. Found: C, 38.05; H, 3.8; N, 3.2; S, 11.5.
1
LM=112 V−1 cm2 mol−1. H-NMR, l: 9.20 (d, 1H),
7.8 (t, 1H), 7.69 (d, 1H), 7.54 (t, 1H), 7.2–7.5 (m, br,
10H), 1.96 (d, J (PH)=6.3 Hz). 31P{1H}-NMR, l:
−6.6 (dd, J 109AgP=732.4, J 107AgP=633.8 Hz). 6:
yield 52%. Anal. Calc. for C31H33AgB10F3N2O3S3: C,
40.2; H, 3.6; N, 3.0; S,10.45. Found: C, 40.65; H, 3.7;
4.8; N, 7.55; S, 17.7. LM=3 V−1 cm2 mol−1 1H-
.
N, 2.5; S, 9.6. LM=114 V−1 cm2 mol−1 1H-NMR,
.
l: 7.3–7.5 (m, br, 15H), 7.92 (m, br, 1H), 7.73 (m,
br, 2H), 7.67 (m, br, 1H).
NMR: l=8.62 (dd, 1H), 7.72 (m, br, 2H), 7.32 (m,
br, 1H).
3.2. [Ag(OTf){1,2-(C5H4NS)2-1,2-C2B10H10}] (2)
3.5. [Au2{1,2-(C5H4NS)2-1,2-C2B10H10}(PPh3)2](OTf)2
(7)
To a solution of 1,2-(C5H4NS)2-1,2-C2B10H10 (0.036
g, 0.1 mmol) in dichloromethane (20 cm3) a solution
of AgOTf (0.1 mmol, 0.025 g) in Et2O (10 cm3) was
added. The mixture was stirred for 30 min and the
solution concentrated to ca. 5 cm3. Addition of hex-
ane (10 cm3) gave complex 2 as a white solid. Yield,
78%. Anal. Calc. for C13H18AgB10F3N2OS3: C, 25.2;
H, 2.9; N, 4.5; S, 15.5. Found: C, 24.9; H, 3.2; N,
To a solution of [Au(OTf)(PPh3)] (0.062 g, 0.1
mmol) in dichloromethane (20 cm3), 1,2-(C5H4NS)2-
1,2-C2B10H10 (0.036 g, 0.1 mmol) was added. The
mixture was stirred for 30 min. Concentration of sol-
vent to ca. 5 cm3 and addition of hexane (10 cm3)
afforded complex 7 as a white solid. Yield, 70%.
Anal. Calc. for C50H66Au2B10F6N2O6P2S2: C, 38.0; H,
3.1; N, 1.75; S, 8.1. Found: C, 38.5; H, 2.65; N, 1.8;
4.3; S, 15.2. LM=91 V−1 cm2 mol−1 1H-NMR, l:
.
8.74 (dd, 1H), 7.93 (td, 1H), 7.71 (d, 1H), 7.55 (td,
1H).
S, 7.8. LM=138 V−1 cm2 mol−1 1H-NMR, l: 7.3–
.
7.5 (m, br, 30H), 8.99 (m, br 1H), 8.35 (m, br, 2H),
7.96 (m, br, 1H). 31P{1H}-NMR, l: 34.6 (s, br).
3.3. [Ag{1,2-(C5H4NS)2-1,2-C2B10H10}2]OTf (3)
3.6. Crystal structure determination of complex 4
To a solution of 1,2-(C5H4NS)2-1,2-C2B10H10 (0.072
g, 0.2 mmol) in dichloromethane (20 cm3), a solution
of AgOTf (0.1 mmol, 0.050 g) in Et2O (10 cm3) was
added. The mixture was stirred for 30 min and the
solution concentrated to ca. 5 cm3. Addition of hex-
ane (10 cm3) gave complex 3 as a white solid. Yield,
69%. Anal. Calc. for C25H36AgB20F3N4O3S5: C, 30.95;
H, 3.7; N, 5.7; S, 16.0. Found: C, 30.45; H, 3.2; N,
3.6.1. Crystal data
4: C31H33AgB10F3N2O3PS3, Mr=881.71, mono-
clinic, space group P21/c, a=15.647(1), b=15.411(1),
3
˚
˚
c=16.190(1) A, i=95.439(7)°, V=3886.4(4) A ,
Z=4, Dcalc=1.507 Mg m−3, u(Mo–Kh)=0.71073 A,
˚
v=0.772 mm−1, F(000)=1776, T= −100°C.

18
O. Crespo et al. / Journal of Organometallic Chemistry 561 (1998) 13–18
References
3.6.2. Data collection and reduction
Single crystals were obtained by slow diffusion of
hexane into a dichloromethane solution of complex 4.
A colourless prism 0.40×0.30×0.25 mm was used to
collect 9388 intensities to 2qmax 50° (Siemens P4 dif-
fractometer, monochromated Mo–Kh radiation) of
which 6836 were independent (Rint=0.030). Cell con-
stants were refined from 2q values of 75 reflections in
the range 10–25°. An absorption correction was ap-
plied on the basis of C-scans (transmission factors
0.750–0.831).
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3.6.3. Structure solution and refinement
Structure was solved by direct methods and refined
on F2 using the program SHELXL-93 [18]. All non-hy-
drogen atoms were refined anisotropically. Refinement
proceeded to wR (F2) 0.0634 for 6830 reflections and
487 parameters. Conventional R(F) 0.0299; S(F2)
−3
˚
0.857; Dz=0.568 e A
.
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4. Supplementary material available
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Full details of the crystal structure determination can
be ordered from Fachinformationszentrun Karlsruhe,
76344 Eggenstein-Leopoldshafen, under the depositary
number CSD-407191.
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[18] G.M. Sheldrick, SHELXL-93, Program for Crystal Structure
Refinement, University of Go¨ttingen, 1993.
Acknowledgements
We thank the Direccio´n General de Investigacio´n
Cient´ıfica y Te´cnica (No. PB94-0079) for financial
support.
.