Gold ACHTUNGTRENNUNG( III) Complexes
+
ꢀ
calculated at the optimized geometries at the same level of theory. Elec-
tronic-transition energies and oscillator strengths were calculated at the
TD-DFT level (200 states). The electronic spectra were simulated by a
convolution of Gaussian functions centred at the calculated excitation en-
ergies. All calculations were carried out on a 64-bit E4 workstation
equipped with four quad-core AMD Opteron processors and 16 Gb of
RAM and running the OpenSuSE 10.2 Linux operating system.
Synthesis of (TBA )(1 )
An ethyl alcohol solution of KOH (40 mL; 0.17 g, 3.1 mmol) was added
dropwise to 4-phenyl-[1,3]dithiol-2-one (30 mL EtOH; 0.25 g, 1.30 mmol)
under an inert atmosphere. After addition of solutions of KAuCl
4
+
ꢀ
(
15 mL; 0.25 g, 0.67 mmol) and (TBA )(I ) (15 mL; 0.25 g, 0.69 mmol)
in ethyl alcohol, the volume of the reaction mixture was reduced and the
precipitate was collected by filtration. Yield 0.12 g (24%); m.p. 1288C;
FTIR: n˜ =2958 (vw), 2870 (vw), 1718 (s), 1590 (w), 1571 (w),1538 (s),
Synthesis of O-Isopropyl S-Phenyl Dithiocarbonate
ꢀ
1
1
484 (s), 1440 (w), 1375 (vw), 1140 (vs), 746 (s), 691 cm (s); UV/Vis/
A solution of 2-bromo-2’-acetophenone (4.15 g, 20.86 mmol) in acetone
NIR (CH
(
2
Cl
2
ꢀ1
):
l
(e)=269 (35000), 296 sh (32000), 346 nm
Au: C 49.79,
(
2
40 mL) was added dropwise to potassium isopropyl xanthate (3.64 g,
0.86 mmol) dissolved in the same solvent (200 mL). After one hour of
ꢀ1
12800m cm ); elemental analysis calcd (%) for C32
H 6.27, N 1.81, S 16.61; found: C 49.66, H 5.51, N 1.51, S 15.15.
H
48NS
4
stirring, the solution was filtered through celite. After concentration
under reduced pressure, an equivalent volume of water was added. The
product was filtered, washed with water and subsequently with hexane,
and dried under reduced pressure. Yield: 4.50 g (84%); m.p. 658C;
FTIR: n˜ =3061 (w), 2987 (w), 2930 (vw), 1692 (vs), 1594 (m), 1578 (m),
+
ꢀ
Synthesis of (TBA )(2 )
+
ꢀ
+
ꢀ
AHCTUNGTRENNUNG
(
1
1
447 (s), 1373 (m), 1352 (m), 1325 (m), 1228 (s), 1093 (m), 1047 (m), 984
ꢀ
1
ꢀ
1
855 (vw), 815 (m), 780 (m), 748 cm (m); UV/Vis/NIR (CH
2
Cl
47 (65500), 295 sh (36000), 365 nm (13000m cm ); elemental analysis
calcd (%) for C40 Au: C 55.09, H 6.01, N 1.61, S 14.71; found: C
54.57, H 6.33, N 1.67, S 14.38.
2
): l (e)=
(
m), 904 (m), 872 (m), 750 cm (s); elemental analysis calcd (%) for
: C 56.67, H 5.55, S 25.21; found: C 56.60, H 5.65, S 24.39.
ꢀ
1
ꢀ1
2
12 14 2 2
C H O S
H
52NS
4
Synthesis of O-Isopropyl S-Naphthacyl Dithiocarbonate
+
ꢀ
The synthesis was carried out as described for O-isopropyl-S-phenyldi-
thiocarbonate starting from 2-bromo-2’-acetonaphthone (2.04 g,
Synthesis of (TBA )(3 )
+
ꢀ
+
ꢀ
AHCTUNGTRENNUNG
8
.20 mmol). Yield: 2.24 g (92%); m.p. 998C; FTIR: n˜ =2980 (vw), 2919
(
(
(
vw), 1692 (s), 1624 (w), 1347 (w), 1224 (vs), 1146 (w), 1128 (vw), 1094
s), 1050 (s), 1026 (w), 823 cm (w); elemental analysis calcd (%) for
: C 63.13, H 5.30, S 21.06; found: C 63.06, H 5.77, S 21.57.
ꢀ
1
ꢀ
1
8
3
16 cm (m); UV/Vis/NIR (CH2Cl2): l (e)=245 (99000), 282 (67500),
16 16 2 2
C H O S
ꢀ
1
ꢀ1
52 (43500), 435 sh nm (7400m cm ); elemental analysis calcd (%) for
Au: C 61.22, H 5.53, N 1.37, S 12.57; found: C 61.01, H 5.40, N
.14, S 12.30.
Synthesis of O-Isopropyl S-Pyrenacyl Dithiocarbonate
52 4
C H20NS
1
The synthesis was carried out as described for O-isopropyl-S-phenyldi-
thiocarbonate starting from 1-(bromoacetyl)pyrene (2.01 g, 3.10 mmol).
Yield: 0.81 g (68%); m.p. 116–1188C; FTIR: n˜ =2987 (vw), 1676 (m),
Supporting Information
Tables giving details of the data collection and refinement, atomic coordi-
1
1
592 (w), 1371 (vw), 1383 (w), 1371 (vw), 1258 (vw), 1234 (m), 1216 (vw),
+
ꢀ
ꢀ
1
nates, displacement parameters, bond lengths and angles for (TBA )(2 ),
optimized geometries in Cartesian coordinate format, frontier KS-MO
energies, TD-DFT vertical transition energies, vibrational IR and Raman
177 (w), 1087 (s), 1045 (vs), 991 (w), 959 (vw), 842 cm (vs); elemental
: C 69.81, H 4.79, S 16.94; found: C
analysis calcd (%) for C22
9.02, H 5.12, S 17.33.
18 2 2
H S O
6
ꢀ
ꢀ
frequencies calculated for the cis and trans isomers of 1 , 1, 2 , and 2 are
Synthesis of Phenyl-[1,3]dithiol-2-one
available on request from the author.
Perchloric acid (3.0 mL, 65% w/w) was slowly added to a solution of O-
isopropyl S-phenyl dithiocarbonate (2.53 g, 9.96 mmol) in a 1:2 diethyl
ether/chloroform mixture (18 mL). The reaction mixture was heated at
reflux for one hour and then poured into ice water. The organic phase,
extracted with chloroform, was dried with Na
solvent was removed under reduced pressure. Yield: 1.66 g (86%); m.p.
2 4
SO . After filtration, the
Acknowledgements
9
1
08C; FTIR: n˜ =3089 (vw), 1958 (vw), 1749 (w), 1697 (vw), 1647 (s),
ꢀ
1
Dr. Luca Pala is acknowledged for his contribution to this work. The
Ministero dell’Istruzione, dell’Universitꢁ e della Ricerca (MIUR) is ac-
knowledged for financial support (PRIN 2007-C8RW53). M.B.H. and
S.L.H. thank the UK EPSRC for support of the X-ray facilities at South-
ampton.
578 (vw), 1487 (m), 1443 (m), 1099 (m), 1074 (m), 874 (s), 743 cm
O: C 55.64, H 3.11, S 33.01;
(
vs); elemental analysis calcd (%) for C
9
H
6
S
2
found: C 55.69, H 3.19, S 32.60.
Synthesis of Naphthyl-[1,3]dithiol-2-one
The synthesis was carried out as described for phenyl-[1,3]dithiol-2-one
starting from O-isopropyl S-naphthacyl dithiocarbonate (2.51 g,
[
1] M. Arca, M. C. Aragoni in Handbook of Chalcogen Chemistry: New
Perspectives in Sulfur, Selenium, and Tellurium (Ed.: F. A. Devilla-
8
.24 mmol). Yield: 1.72 g (86%); m.p. 1458C; FTIR: n˜ =3089 (vw), 3051
(
8
vw), 1741 (vw), 1708 (vw), 1633 (vs), 1503 (vw), 1361 (vw), 1204 (w),
ꢀ
1
88 (m), 860 (m), 776 (m), 754 cm (m); elemental analysis calcd (%)
O: C 63.91, H 3.30, S 26.24; found: C 63.56, H 3.55, S 25.49.
[
3] C. Faulmann, P. Cassoux, Prog. Inorg. Chem. 2004, 52, 399–489.
4] C. L. Beswick, J. A. Schulman, E. I. Stiefel, Prog. Inorg. Chem. 2004,
for C13
8 2
H S
[
[
Synthesis of 4-Pyrenyl-[1,3]dithiol-2-one
The synthesis was carried out as described for phenyl-[1,3]dithiol-2-one
starting from O-isopropyl S-pyrenacyl dithiocarbonate (0.70 g,
5
2, 55–110.
5] M. L. Kirk, R. L. McNaughton, M. E. Helton, Prog. Inorg. Chem.
004, 52, 111–212.
[
1
.86 mmol). Yield: 0.55 g (93%); m.p. 1308C; FTIR: n˜ =3038 (w), 2962
2
ꢀ
1
(
w), 1685 (m), 1644 (s), 844 (vs), 816 (w), 748 (w), 711 cm (s); elemen-
tal analysis calcd (%) for C19 O: C 71.67, H 3.17, S 20.14; found: C
9.39, H 3.36, S 19.61.
[
[
6] K. Wang, Prog. Inorg. Chem. 2004, 52, 267–314.
10 2
H S
7] M. C. Aragoni, M. Arca, M. Caironi, C. Denotti, F. A. Devillanova,
6
[
8] S. D. Cummings, R. Eisemberg, Prog. Inorg. Chem. 2004, 52, 315–
3
67.
Chem. Asian J. 2010, 5, 1395 – 1406
ꢂ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1405