E. J. Fernández, A. Laguna et al.
FULL PAPER
(5) and NO2 (6)]: To a dichloromethane solution (20 mL) of the
benzenethiol (0.337 mmol) was added an excess amount of NaOMe
(0.073 g, 1.34 mmol). After 15 min of stirring, complex
ence of aurophilic interactions as well as the electron-with-
drawing ability of the substituents in the 4-position of the
benzenethiolato ligands were studied. It seems plausible
that the electron-withdrawing abilities of the substituents in
4-position of the benzenethiolato ligand do not play a key
role as it is not possible to correlate it with the emission
energies. The results obtained could be more likely related
to the presence of aurophilic interactions in the complexes,
although the possibility of a contribution of the substitu-
ents to the excited state cannot be neglected.
[Au4Cl4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}]
1
was added
(0.15 g, 0.084 mmol). The reaction mixture was stirred for 2 h, gen-
erating a white solid (NaCl) that was separated by filtration. The
filtrate was evaporated to ca. 5 mL, and the addition of diethyl
ether (20 mL) led to the precipitation of the compounds.
3: From 4-fluorobenzenethiol (0.043 g). Yield: 45%, white solid. 1H
NMR (300 MHz, CDCl3): δ = 7.70–7.20 (m, 40 H, Ph rings), 6.77
(m, 8 H, 3-H and 5-H in S-C6H4-F), 3.83 (s, 8 H, PCH2N), 2.61
(s, 4 H, NCH2CH2N) ppm.31P{1H} NMR (121 MHz, CDCl3): δ =
23.5 (s) ppm. 19F NMR (283 MHz, CDCl3): δ = –120.70 (s, 4 F)
ppm. IR:
ν =
1584 ν(C–N), 1103, 857 ν(C–S) cm–1. MS
˜
Experimental Section
(MALDI+): m/z (%) = 2022 (1.5) [M – (S-C6F4-F)]+, 1698 (17)
[M – Au(S-C6H4-F)2]+. C78H68Au4F4N2P4S4 (2149.41): calcd. C
43.58, H 3.19, N 1.30, S 5.97; found C 43.33, H 3.16, N 1.35, S
5.90.
General: The compounds [AuCl(tht)],[16] [Au(C6F5)(tht)][17] and
[8]
(Ph2PCH2)2NCH2CH2N(CH2PPh2)2 were synthesized by stan-
dard literature procedures. The starting materials Ph2PH, p-form-
aldehyde and NH2CH2CH2NH2 were purchased from Sigma–
Aldrich and used as received without further purification.
4: From 4-methoxybenzenethiol (0.047 g). Yield: 63%, yellow solid.
1H NMR (300 MHz, CDCl3): δ = 7.70–7.20 (m,40 H, Ph rings),
7.41 (m, 8 H, 2-H and 6-H in S-C6H4-OCH3), 6.64 (m, 8 H, 3-H
and 5-H in S-C6H4-OCH3), 3.83 (s, 8 H, PCH2N), 3.69 (s, 12 H,
MeO), 2.57 (s, 4 H, NCH2CH2N) ppm. 31P{1H} NMR (121 MHz,
Instrumentation: Infrared spectra were recorded in the 4000–
200 cm–1 range with a Perkin–Elmer FTIR Spectrum 1000 spectro-
photometer by using Nujol mulls between polyethylene sheets. C,
H and N analyses were carried out with a C.E. Instrument EA-
1110 CHNS-O microanalyzer. Mass spectra were recorded with a
MICROFLEX MALDI-TOF spectrometer by using dithranol
(DIT) as matrix. 1H, 19F and 31P{1H} NMR spectra were recorded
with a Bruker ARX 300 in CDCl3. Chemical shifts are quoted rela-
tive to SiMe4 (1H external), CFCl3 (19F external) and H3PO4 (85%)
(31P external), respectively. Excitation and emission spectra as well
as lifetime measurements were recorded with a Jobin–Yvon Horiba
Fluorolog 3–22 Tau-3 spectrofluorimeter.
CDCl ): δ = 23.4 (s) ppm. IR: ν = 1589 ν(C–N), 1101, 867 ν(C–S)
˜
3
cm–1. MS (MALDI+): m/z (%) = 2058 (4) [M – (S-C6H4-OCH3)]+,
1722 (28) [M
–
Au(S-C6H4-OCH3)2]+. C82H80Au4N2O4P4S4
(2197.55): calcd. C 44.82, H 3.67, N 1.27, S 5.84; found C 44.58,
H 3.45, N 1.26, S 5.54.
5: From 4-methylbenzenethiol (0.042 g). Yield: 51%, yellow solid.
1H NMR (300 MHz, CDCl3): δ = 7.70–7.20 (m,40 H, Ph rings),
7.42 (m, 8 H, 2-H and 6-H in S-C6H4-CH3), 6.87 (m, 8 H, 3-H and
5-H in S-C6H4-CH3), 3.82 (s, 8 H, PCH2N), 2.59 (s, 4 H,
NCH2CH2N), 2.21 (s, 12 H, Me) ppm. 31P{1H} NMR (121 MHz,
[Au4Cl4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}] (1): To a dichloro-
methane solution (20 mL) of [AuCl(tht)] (0.20 g, 0.624 mmol) in
dichloromethane (20 mL) was added (Ph2PCH2)2NCH2-
CH2N(CH2PPh2)2 (0.13 g, 0.145 mmol). After 30 min of stirring at
room temp., the solvent was evaporated to ca. 5 mL. The addition
of n-hexane (20 mL) led to the precipitation of compound 1 as a
white solid. Yield: 83%. 1H NMR (300 MHz, CDCl3): δ = 7.80–
7.20 (m, 40 H, aromatic protons), 3.87 (s, 8 H, P-CH2-N), 2.60 (s,
4 H, N-CH2CH2-N) ppm. 31P{1H} NMR (121 MHz, CDCl3): δ =
CDCl ): δ = 23.5 (s) ppm. IR: ν = 1587 ν(C–N), 1101, 867 ν(C–S)
˜
3
cm–1. MS (MALDI+): m/z (%) = 2010 (1) [M – (S-C6H4-
CH3)]+, 1690 (2) [M – Au(S-C6H4-CH3)2]+. C82H80Au4N2P4S4
(2133.55): calcd. C 46.16, H 3.78, N 1.31, S 6.01; found C 46.12,
H 3.62, N 1.36, S 5.98.
6: From 4-nitrobenzenethiol (0.052 g). Yield: 80%, orange solid.
1H NMR (300 MHz, CDCl3): δ = 7.60–7.40 (m,40 H, Ph rings),
7.82 (m, 8 H, 3-H and 5-H in S-C6H4-NO2), 7.37 (m, 8 H, 2-H and
6-H in S-C6H4-NO2), 3.81 (s, 8 H, PCH2N), 2.89 (s, 4 H,
NCH2CH2N) ppm. 31P{1H} NMR (121 MHz, CDCl3): δ = 23.5 (s)
17.7 (s, PPh ) ppm. IR: ν = 1573 ν(C–N), 327 ν(Au–Cl) cm–1. MS
˜
2
(MALDI+): m/z (%) = 1747.1 (100) [M – Cl]+. C54H52Au4Cl4N2P4
(1782.57): calcd. C 36.38, H 2.94, N 1.57; found C 36.52, H 2.97,
N 1.59.
ppm. IR: ν = 1569 ν(C–N), 1499, 1328 ν(C–NO ), 1103, 857 ν(C–
˜
2
S) cm–1. MS (MALDI+): m/z (%) = 2103 (1) [M – (S-C6H4-
NO2)]+, 1752 (11) [M – Au(S-C6H4-NO2)2]+. C78H68Au4N6O8P4S4
(2257.43): calcd. C 41.49, H 3.03, N 3.72, S 5.68; found C 41.46,
H 2.93, N 3.91, S 5.89.
[Au4(C6F5)4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}] (2): To
a
dichloromethane solution (20 mL) of [AuC6F5(tht)] (0.15 g,
0.332 mmol) in dichloromethane (20 mL) was added (Ph2PCH2)2-
NCH2CH2N(CH2PPh2)2 (0.071 g, 0.083 mmol). After 30 min of
stirring at room temp., the solvent was evaporated to ca. 5 mL. The
addition of n-hexane (20 mL) led to the precipitation of compound
Crystallography: The crystals were mounted in inert oil on glass
fibres and transferred to the cold gas stream of a Nonius Kappa
CCD diffractometer equipped with an Oxford Instruments low-
temperature attachment. Data were collected by monochromated
Mo-Kα radiation (λ = 0.71073 Å). Scan type ω and φ. Absorption
corrections: numerical (based on multiple scans). The structures
were solved by direct methods and refined on F2 by using the pro-
gram SHELXL-97.[18] All non-hydrogen atoms were anisotropically
refined with the exception of the solvent (diethyl ether) molecule
in 2. Hydrogen atoms were included using a mixed model. CCDC-
647628 to -647629 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
1
2 as a white solid. Yield: 75%. H NMR (300 MHz, CDCl3): δ =
7.70–7.20 [m, 40 H, aromatic protons], 3.70 (s, 8 H, P-CH2-N), 3.02
(s, 4 H, N-CH2CH2-N) ppm. 31P{1H} NMR (121 MHz, CDCl3): δ
= 24.7 (s, PPh2) ppm. 19F NMR (283 MHz, CDCl3): δ = –115.36
(m, 8 F, Fortho), –157.71 (t, 3JFp-Fm = 19 Hz, 4 F, Fpara), –161.82 (m,
8 F, Fmeta) ppm. IR: ν = 1586 ν(C–N), 1504, 954, 792 ν(Au–C F )
˜
6
5
cm–1. MS (MALDI+): m/z (%) = 1777.9 (100) [M – Au(C6F5)2]+.
C78H52Au4F20N2P4 (2308.99): calcd. C 40.57, H 2.27, N 1.21;
found C 40.96, H 2.38, N 1.25.
General Procedure for the Preparation of [Au4(S-C6H4-X)4-
{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}] [X = F (3), MeO (4), Me
4004
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Eur. J. Inorg. Chem. 2007, 4001–4005