Tetranuclear (phosphane)(thiolato)gold(I) complexes: Synthesis, characterization and photoluminescent properties

Article abstract of DOI:10.1002/ejic.200700529

The reactions of the tetraphosphane donor ligand (Ph₂PCH ₂)₂NCH₂CH₂N(CH₂PPh ₂)₂ with the gold precursors [AuCl(tht)] or [Au(C ₆F₅)(tht)] (tht = t

Full text of DOI:10.1002/ejic.200700529

FULL PAPER
DOI: 10.1002/ejic.200700529
Tetranuclear (Phosphane)(thiolato)gold(I) Complexes: Synthesis,
Characterization and Photoluminescent Properties
Eduardo J. Fernández,*[a] Antonio Laguna,*[b] José M. López-de-Luzuriaga,[a]
Miguel Monge,[a] Manuel Montiel,[a] M. Elena Olmos,[a] Raquel C. Puelles,[a] and
Eva Sánchez-Forcada[a]
Dedicated to Professor Vicente Gotor on the occasion of his 60th birthday
Keywords: Phosphanes / Thiolates / Gold / Luminescence / Aurophilicity
The reactions of the tetraphosphane donor ligand (Ph2PCH2)2-
NCH2CH2N(CH2PPh2)2 with the gold precursors [AuCl(tht)]
Au···Au interactions in the case of complex 4. Complexes 3–
6 display intense emissions in the solid state at 77 K with
or [Au(C6F5)(tht)] (tht = tetrahydrothiophene) leads to com- lifetimes in the microsecond range. The observed phospho-
plexes [Au4R4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}] [R = Cl
(1) or C6F5 (2)]. Further substitution of the chlorine atoms in
1 by the corresponding 4-substituted benzenethiolates gives
rescent emissions are attributed to metal-to-ligand charge-
transfer transitions. Nevertheless, the influence in the emis-
sion energies of gold–gold interactions or the contribution of
rise to the tetranuclear (phosphane)(thiolato)gold(I) com- the substituent in the 4-position of the benzenethiolate ring
plexes [Au4(S-C6H4-X)4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}]
[X = F (3), MeO (4), Me (5) and NO2 (6)]. Complexes 2 and
4 were characterized by X-ray diffraction studies showing
to the excited state cannot be neglected.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
Introduction
parable in strength with hydrogen bonding, are recognized
as a structural motif that governs the amazing molecular
and supramolecular arrangements found in the solid state
for many types of gold(I) compounds.[5] Moreover, several
(phosphane)(thiolato)gold(I) compounds also display very
interesting photoluminescent properties over a wide range
of the visible spectrum (400–700 nm), and the observed
emissions are usually attributed to ligand-to-metal charge-
transfer (LMCT) excited states that can be perturbed by the
presence of the above-mentioned AuI···AuI interactions.[6]
In spite of several literature reports[7] on the synthesis of
(phosphane)(thiolato)gold(I) complexes, the quest for high
nuclearity compounds is often pursued through the use of
Polynuclear gold(I) complexes have attracted much inter-
est in the last years mainly due to their intriguing structural
dispositions, their rich photoluminescent properties[1] or
even their potential applications in different fields as phar-
maceutics, optical sensors, chemosensing, etc. In this sense,
much of the interest has been generated by the clinical use
of the mononuclear (phosphane)(thiolato)gold complex
Auranofin,[2] employed in the treatment of reumathoid ar-
thritis. Also, these types of complexes can be used as optical
sensors for volatile organic compounds (VOCs) as shown
by Eisenberg and coworkers[3] or as specific sensors for sev-
eral cations as reported by Yam et al.[4]
(Thiolato)gold(I) complexes containing multidentate
phosphane ligands can be considered an important class of
polynuclear compounds, as the presence of several P–Au–S
structural units in their structures permits the formation of
aurophilic interactions. These interactions, which are com-
[a] Departamento de Química, Universidad de La Rioja, Grupo de
Síntesis Química de La Rioja, UA-CSIC – Complejo Científico-
Tecnológico,
26004 Logroño, Spain
Fax: +34-941-299-621
E-mail: eduardo.fernandez@unirioja.es
[b] Departamento de Química Inorgánica, Instituto de Ciencia de
Materiales de Aragón, Universidad de Zaragoza – CSIC,
50009 Zaragoza, Spain
Scheme 1. Synthesis of complexes 1–6. (i) [Au(C6F5)(tht)]; (ii)
[AuCl(tht)]; (iii) NaOMe, SH–C6H4–X (X = F, OMe, Me or NO2).
Fax: +34-976-761-187
E-mail: alaguna@unizar.es
Eur. J. Inorg. Chem. 2007, 4001–4005
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4001

E. J. Fernández, A. Laguna et al.
FULL PAPER
bi- or tridentate phosphorus donor ligands. We focused a X-ray Structural Determination of Derivatives 2 and 4
part of our outgoing research on the synthesis of high nu-
Single crystals suitable for X-ray diffraction studies were
clearity gold(I) complexes through the reaction of the ap-
obtained by layering diethyl ether or hexane into a solution
propriate gold(I) precursors with the tetradentate P donor
of the complex in dichloromethane (for 2) or toluene (for
4). Both 2 and 4 crystallize in the P1 space group of the
[8]
ligand (Ph2PCH2)2NCH2CH2N(CH2PPh2)2 that permits
¯
the synthesis of tetranuclear (phosphane)(thiolato)gold(I)
compounds (Scheme 1).
triclinic system with one molecule of the complex and one
half of a molecule of diethyl ether (for 2) or one molecule
of toluene (for 4) in the unit cell. Both structures consists
of tetranuclear molecules in which each phosphorus atom
of the tetradentate phosphane binds a (pentafluorophenyl)-
gold(I) unit or a (thiolato)gold(I) unit for 2 and 4, respec-
tively (Figures 1 and 2), with Au–P distances of 2.2725(14)
and 2.2799(14) Å for 2 and 2.260(2) and 2.267(2) Å for 4,
which compare well to those found in other related
(pentafluorophenyl)-[9] or (benzenethiolato)(phosphane)-
gold(I)[6a,10,12] complexes. The gold(I) centres complete
their usual lineal environment with the coordination of a
carbon atom of the anionic ligand C6F5 or a sulfur atom
of S–C6H4–OMe for 2 or 4, respectively. The Au–C bonds
In this paper we report the synthesis of tetranuclear
(phosphane)(thiolato)gold(I) compounds that are brightly
luminescent in the solid state at 77 K. We analyzed the
mechanism responsible for the luminescence in this type of
complex by taking into account the presence of intramolec-
ular aurophilic interactions or the electronic influence of
the substituent in the 4-position of the benzenethiolato li-
gands bonded to gold.
Results and Discussion
Synthesis and Characterization
The tetranuclear gold(I) compounds [Au4R4{(Ph2PCH2)2-
NCH2CH2N(CH2PPh2)2}] [R = Cl (1) or C6F5 (2)] were
prepared by the reaction of 4 equiv. of the corresponding
[AuCl(tht)] or [Au(C6F5)(tht)] (tht = tetrahydrothiophene)
precursors and 1 equiv. of the tetradentate phosphane li-
gand (Ph2PCH2)2NCH2CH2N(CH2PPh2)2 (Scheme 1) in
quantitative yields by displacement of the labile tht ligand
as crystalline white solids. All analytical and spectroscopic
data are in agreement with the proposed stoichiometries.
Their 31P{1H} NMR spectra display a singlet at 17.7 (1)
or 24.7 ppm (2), which shows a large shift downfield upon
coordination of the four Cl–Au or C6F5–Au units to the
tetraphosphane ligand (–28.5 ppm). The 19F NMR spec-
trum of complex 2 shows the expected pattern of the C6F5
groups bonded to AuI with three signals at –115.4, –157.7
and –161.8 ppm, which correspond to the fluorine atoms in
the ortho, para and meta positions, respectively. Both com-
Figure 1. Molecular structure of complex 2. Selected bond lengths
[Å] and angles [°]: Au1–C1 2.049(6), Au2–C11 2.051(6), Au1–P1
plexes show the corresponding signals of the different meth- 2.2725(14), Au2–P2 2.2799(14), C1–Au1–P1 174.74(15), C11–Au2–
P2 175.81(16).
ylene groups that are present in the phosphane ligand in
their H NMR spectra, and they are also shifted downfield
1
relative to those of the free ligand. Their IR spectra show
absorptions arising from the Au–Cl or Au–C6F5 groups
that appear at 326 or at 1504, 954 and 792 cm–1.
The reaction of complex 1 with different 4-substituted
benzenethiols affords the corresponding compounds
[Au4(S–C6H4-X)4{(Ph2PCH2)2NCH2CH2N(CH2PPh2)2}]
[X = F (3), MeO (4), Me (5) and NO2 (6)] as stable crystal-
line solids. The thiolato ligands are prepared in situ by the
reaction of the benzenethiols with an excess amount of so-
dium methoxide. The analytical and spectroscopic proper-
ties are in accordance with the proposed formulations.
Their 31P{1H} NMR spectra show very similar shifts for
the corresponding singlets as a result of the similar chemi-
cal and magnetic environments around the P atoms at 23.5,
23.4, 23.5 and 23.5 ppm for complexes 3–6, respectively. In
Figure 2. Molecular structure of complex 4. Selected bond lengths
all cases, their IR spectra display the characteristic absorp-
[Å] and angles [°]: Au1–S1 2.318(2), Au2–S2 2.313(2), Au1–P1
2.260(2), Au2–P2 2.267(2), Au1–Au2 3.1485(4), S1–Au1–P1
169.13(8), S2–Au2–P2 173.13(7).
tions due to ν(C–S) at 1103, 857 (for 3), 1101, 867 (for 4),
1101, 867 (for 5) and 1103, 857 cm–1(for 6).
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Tetranuclear (Phosphane)(thiolato)gold(I) Complexes
FULL PAPER
in 2, of 2.049(6) and 2.051(6) Å, show typical values for
pentafluorophenylphosphane gold(I) complexes,[9] whereas
the Au–S bond lengths in 4 [2.318(2) and 2.313(2) Å] are
slightly longer than the values found in a great number of
(benzenethiolato)(phosphane)gold(I) complexes, but they
are nearly identical to those observed in some derivatives
containing the fragment Ph–S–Au–P. [6a,10a,10b,11] The main
difference between these two structures is that whereas in 4
the metals associate into pairs through weak intramolecular
Au···Au interactions of 3.1485(4) Å, the same disposition is
not found in the case of complex 2, in which the shortest
Au–Au distance is 4.264 Å. The Au–Au distance in 4 is
shorter than that in the related (diphosphane)(thiolato)-
gold(I) complexes [Au2(S–B15C5)2(dcmp)] [dcmp = bis(di-
cyclohexylphosphanyl)methane, S–B15C5 = 4Ј-mercapto-
benzo-15-crown-5] [3.2556(8) Å] or [Au2(dcmp)(S–B18C6)2]
(S–B18C6 = 4Ј-mercaptobenzo-18-crown-6) [3.284(1) Å],[12]
but it is longer than that in [Au2(m-tc)2{Ph2P(o-C6H4)O(o-
C6H4) PPh2}] (tc = thiocresol) [3.0065(15) Å],[13] [Au2(S–
C6H4NH2-2)2(dppm)] [3.1346(4) Å][6b] or [Au2(S–C6H4-
CONH2-2)2(dppp)] [dppp = bis(diphenylphosphanyl)pro-
pane] [2.9997(7) Å].[10a]
Figure 3. Emission spectra of complexes 3–6.
gands and the presence or absence of gold–gold interactions
in the complexes. Electron-withdrawing groups on the thiol-
ato ligand stabilize the sulfur orbital, which makes the li-
gand more difficult to oxidize and shifts the emissions to
higher energies. By contrast, from these studies it was also
concluded that the “gold–gold interaction is not a necessary
condition for luminescence”,[15] but “in some circumstances
shift the emission maxima to lower energies”.[6a] In our
case, only the methoxy derivative was structurally charac-
terized, and the metal–metal distance is 3.15 Å. As the
emission band of the methyl derivative appears at similar
energy and the electron withdrawing capability is similar for
both groups, it is likely that this complex will display a sim-
ilar gold–gold interaction. Nevertheless, when a fluorine
atom is the substituent on the thiolato ligand its much
higher electron-withdrawing ability only slightly shifts the
emission band to higher energy; this can be attributed to a
decreased effectiveness of this ability in the para position.
Finally, the nitro derivative displays the longest wavelength
emission in spite of its large electron-withdrawing ability.
By taking into account that it is also placed in the para
position where this effect is diminished, it is likely that the
nitro group importantly contributes to the excited state or
that this derivative presents a very short gold–gold interac-
tion in the solid state.
Photophysical Studies
The four phosphane–sulfide complexes display lumines-
cence under UV light at 77 K, but they are not luminescent
at room temperature or in solution. Thus, by excitation at
375 nm (complexes 3–5) or 475 nm (complex 6), emissions
at 497, 508, 510 or 625 nm, respectively, are observed. The
large Stokes shifts observed (Ͼ6500 for 3, 6900 for 4, 7000
for 5 and 5000 for 6) implies that there is a large distortion
in the excited state relative to the ground state, which is
consistent with a charge transfer transition. In fact, in lumi-
nescent complexes containing S(thiolato)–Au–P(phos-
phane) units, the emissions are assigned to metal-to-ligand
charge transfer (MLCT) transitions and, therefore, we pro-
pose a similar origin.[6] Nevertheless, the presence of phenyl
groups in the ligands raises an alternative assignment, be-
cause emission bands near 500 nm in phenylphosphane
metal complexes have previously been reported. These have
their origin in π–π* transitions,[14] although this possibility
appears remote as the chloro- and pentafluorophenylgold(I)
derivatives 1 and 2, which contain the same diphenylphos-
phane ligand, do not show luminescence neither in the solid
state at different temperatures nor in solution.
Conclusions
We report here the synthesis and characterization of new
tetranuclear (phosphane)(thiolato)gold(I), in which a tetra-
The four complexes have long lifetimes in the microsec- dentate phosphane with an ethylenediamine core and 4-sub-
ond range with values of 28.7 and 107.5 (R2 = 0.997) for 3, stituted benzenethiols are employed as ligands. The X-ray
32.4 (R2 = 0.991) for 4, 30.1 (R2 = 0.991) for 5 and 399.7 µs structure of the precursor gold(I) complex with penta-
(R2 = 0.994) for 6, suggesting that the excited states are of fluorophenyl groups bonded to gold does not show auro-
triplet parentage and, therefore, consistent with phos- philic interactions; meanwhile the corresponding (benzene-
phorescent emissions (Figure 3).
thiolato)(phosphane)gold(I) complex
4
displays two
As regards the position of the emission bands, previous AuI···AuI interactions leading to two pairs of P–Au–S units.
studies in thiolate–phosphane–gold complexes carried out
From the photophysical measurements it was shown that
originally by Bruce et al.[15] and Fackler et al.[6a] point out these (benzenethiolato)(phosphane)gold(I) tetranuclear de-
two main factors that are responsible for the luminescent rivatives display intense luminescence in the solid state at
behaviour: electron-withdrawing groups on the thiolato li- 77 K with lifetimes in the microsecond range. Both the pres-
Eur. J. Inorg. Chem. 2007, 4001–4005
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4003

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
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Eur. J. Inorg. Chem. 2007, 4001–4005

Tetranuclear (Phosphane)(thiolato)gold(I) Complexes
FULL PAPER
e) V. W. W. Yam, E. C. C. Cheng, Z. Y. Zhou, Angew. Chem.
Int. Ed. 2000, 39, 1683; f) Y. Lee, R. Eisenberg, J. Am. Chem.
Soc. 2003, 125, 7778; g) V. W. W. Yam, K. K.-W. Lo, Chem.
Soc. Rev. 1999, 28, 323.
Crystal Data for 2: C78H52Au4F20N2P4·0.5Et2O, Mr = 2346.02, tri-
¯
clinic, P1, a = 12.183(2) Å, b = 14.667(2) Å, c = 14.991(2) Å, α =
116.97(10)°, β = 110.67(10)°, γ = 92.13(10)°, V = 2170.4(5) Å3, Z
= 1, ρcalcd. = 1.795 gcm–3, µ(Mo-Kα) = 6.897 mm–1, R1 = 0.0388,
wR2 = 0.1144 for 10286 observed reflections [IϾ2σ(I)].
[7] M. C. Gimeno, A. Laguna in Comprehensive Coordination
Chemistry II (Eds.: J. A. MacCleverty, T. J. Meyer), Elsevier
Pergamon, 2003, New York, pp. 911–1145 and references cited
therein.
Crystal Data for 4: C82H80Au4N2O4P4S4·C7H8, Mr = 2289.60, tri-
¯
clinic, P1, a = 9.173(2) Å, b = 13.844(3) Å, c = 18.582(5) Å, α =
[8] S. O. Grim, L. J. Matienzo, Tetrahedron Lett. 1973, 14, 2951.
[9] For example, see: a) J. E. Aguado, S. Canales, M. C. Gimeno,
P. G. Jones, A. Laguna, M. D. Villacampa, Dalton Trans. 2005,
3005; b) E. J. Fernández, M. C. Gimeno, P. G. Jones, A. La-
guna, M. Laguna, M. E. Olmos, J. Chem. Soc. Dalton Trans.
1994, 2891; c) M. Bardají, P. G. Jones, A. Laguna, M. D. Villa-
campa, N. Villaverde, Dalton Trans. 2003, 4529; d) M. A.
Bennett, D. C. R. Hockless, A. D. Rae, L. L. Welling, A. C.
Willis, Organometallics 2001, 20, 79; e) O. Crespo, E. J.
Fernández, P. G. Jones, A. Laguna, J. M. López-de-Luzuriaga,
M. Monge, M. E. Olmos, J. Pérez, Dalton Trans. 2003, 1076.
[10] For example, see: a) D. R. Smyth, E. R. T. Tiekink, Z. Kristal-
logr., New Cryst. Struct. 2002, 217, 363; b) J. D. E. T. Wilton-
Ely, A. Schier, N. W. Mitzel, H. Schmidbaur, J. Chem. Soc. Dal-
ton Trans. 2001, 1058; c) T. Yoshida, S. Onaka, M. Shiotsuka,
Inorg. Chim. Acta 2003, 342, 319; d) W. J. Hunks, M. C. Jen-
nings, R. J. Puddephatt, Inorg. Chim. Acta 2006, 359, 3605; e)
B.-C. Tzeng, J. Zank, A. Schier, H. Schmidbaur, Z. Natur-
forsch., Teil B 1999, 54, 825.
105.40(1)°, β = 89.69(1)°, γ = 95.99(1)°, V = 2261.89(9) Å3, Z = 1,
ρcalcd. = 1.681 gcm–3, µ(Mo-Kα) = 6.677 mm–1, R1 = 0.0510, wR2
= 0.1400 for 9289 observed reflections [IϾ2σ(I)].
Acknowledgments
The Dirección General de Investigación MEC/FEDER (CTQ2004-
05495) and European Commission, Interreg III A (NANORET,
I3A-7-341-O) are thanked for financial support. M. Monge thanks
the Ministerio de Educación y Ciencia-Universidad de La Rioja
for his research contract “Ramón y Cajal”. M. Montiel and R. C.
Puelles thank the Comunidad Autónoma de La Rioja and the
Ministerio de Educación y Ciencia for a grant, respectively.
[1] J. M. Forward, J. P. Fackler Jr, Z. Assefa in Optoelectronic
Properties of Inorganic Compounds (Eds.: D. M. Roundhill, J. P.
Fackler Jr), Plenum, 1999, New York, pp. 195–226.
[2] C. F. Shaw III in Gold: Progress in Chemistry, Biochemistry and
Technology (Ed.: H. Schmidbaur), John Wiley & Sons, 1999,
Chichester, pp. 259.
[11] a) K. Nunokawa, K. Okazaki, S. Onaka, M. Ito, T. Sunahara,
T. Ozeki, H. Imai, K. Inoue, J. Organomet. Chem. 2005, 690,
1332; b) R. Narayanaswamy, M. A. Young, E. Parkhurst, M.
Ouellette, M. E. Kerr, D. M. Ho, R. C. Elder, A. E. Bruce,
M. R. M. Bruce, Inorg. Chem. 1993, 32, 2506.
[3] M. A. Mansour, W. B. Connick, R. J. Lachicotte, H. J. Gysling,
R. Eisenberg, J. Am. Chem. Soc. 1998, 120, 1329.
[4] a) V. W. W. Yam, C. L. Chan, C. K. Li, K. M. C. Wong, Coord.
Chem. Rev. 2001, 216–217, 173; b) V. W. W. Yam, C. K. Li,
C. L. Chan, Angew. Chem. Int. Ed. 1998, 37, 2857.
[5] a) H. Schmidbaur, Nature 2001, 413, 31; b) P. Pyykkö, Chem.
Rev. 1997, 97, 597; c) R. J. Puddephatt, Coord. Chem. Rev.
2001, 216–217, 313.
[6] a) J. M. Forward, D. Bohmann, J. P. Fackler Jr, R. J. Staples,
Inorg. Chem. 1995, 34, 6330; b) M. Bardají, M. J. Calhorda,
P. J. Costa, P. G. Jones, A. Laguna, M. R. Pérez, M. D. Villa-
campa, Inorg. Chem. 2006, 45, 1059; c) S. Y. Ho, E. C. C.
Cheng, E. R. T. Tiekink, V. W. W. Yam, Inorg. Chem. 2006, 45,
8165; d) A. Pintado-Alba, H. de la Riva, M. Niewenhuyzen,
D. Bautista, P. R. Raithby, H. A. Sparkes, S. J. Teat, J. M.
López-de-Luzuriaga, M. C. Lagunas, Dalton Trans. 2004, 3459;
[12] C. K. Li, X. X. Lu, K. M. C. Wong, C. L. Chan, N. Zhu,
V. W. W. Ya m , Inorg. Chem. 2004, 43, 7421.
[13] H. de la Riva, A. Pintado-Alba, M. Niewenhuyzen, C. Hard-
acre, M. C. Lagunas, Chem. Commun. 2005, 4970.
[14] J. F. Fife, K. W. Morse, W. M. Moore, J. Photochem. 1984, 24,
249.
[15] W. B. Jones, B. J. Yuan, R. Narayanaswamy, M. A. Young,
R. C. Elder, A. E. Bruce, M. R. M. Bruce, Inorg. Chem. 1995,
34, 1996.
[16] E. A. Allen, W. Wilkinson, Spectrochim. Acta 1972, 28A, 2257.
[17] R. Usón, A. Laguna, J. Vicente, J. Chem. Soc. Chem. Commun.
1976, 353.
[18] G. M. Sheldrick, SHELXL-97: Program for Crystal Structure
Refinement, University of Göttingen, Germany, 1997.
Received: May 21, 2007
Published Online: July 12, 2007
Eur. J. Inorg. Chem. 2007, 4001–4005
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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