Synthesis, coordination to Au(I) and photophysical properties of a novel polyfluorinated benzothiazolephosphine ligand

Article abstract of DOI:10.1039/b517728f

The reaction between Ph₂PH and C₆F₅CNS leads to the formation of the polyfluorinated benzothiazolephosphine ligand Ph₂P(CNS)(C₆F₄) 1. The mechanism of the reaction involves the addition of the phosphine to the isothiocyanate and subsequent intramolecular nucleophilic aromatic substitution. This new ligand reacts with gold(i) substrates producing complexes [AuCl(Ph₂P(CNS) (C₆F₄))] 2 and [Au(C₆F₅)(Ph ₂P(CNS)(C₆F₄))] 3. Both the ligand 1 and complexes 2 and 3 display phosphorescence with emissions arising from n(P) → π*(heterocyclic ring) excited state for 1 and π → π*(heterocyclic ring) excited state for 2 and 3. DFT and TD-DFT calculations agree with these results. The Royal Society of Chemistry 2006.

Full text of DOI:10.1039/b517728f

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PAPER
www.rsc.org/dalton | Dalton Transactions
Synthesis, coordination to Au(I) and photophysical properties of a novel
polyfluorinated benzothiazolephosphine ligand†‡
Eduardo J. Ferna´ndez,*a Antonio Laguna,*b Jose´ M. Lo´pez-de-Luzuriaga,a Miguel Monge,a Manuel Montiel,a
M. Elena Olmosa and Mar´ıa Rodr´ıguez-Castilloa
Received 15th December 2005, Accepted 11th April 2006
First published as an Advance Article on the web 25th April 2006
DOI: 10.1039/b517728f
The reaction between Ph2PH and C6F5CNS leads to the formation of the polyfluorinated
benzothiazolephosphine ligand Ph2P(CNS)(C6F4) 1. The mechanism of the reaction involves the
addition of the phosphine to the isothiocyanate and subsequent intramolecular nucleophilic aromatic
substitution. This new ligand reacts with gold(I) substrates producing complexes
[AuCl{Ph2P(CNS)(C6F4)}] 2 and [Au(C6F5){Ph2P(CNS)(C6F4)}] 3. Both the ligand 1 and complexes 2
and 3 display phosphorescence with emissions arising from n(P) → p*(heterocyclic ring) excited state
for 1 and p → p*(heterocyclic ring) excited state for 2 and 3. DFT and TD-DFT calculations agree with
these results.
Introduction
Polyfunctional molecules bearing P-, N- and/or S-donor centres
are suitable ligands for the coordination of one or various metal
centres leading to homo- or heteropolynuclear compounds. Thus,
it is possible to prepare a broad family of compounds that display
very different structural arrangements and, in some cases, special
physical properties associated with them. These may be used for a
number of special applications including chemotherapy, diagnosis,
electron microscopy and surface technology.1–5
As a part of our ongoing research, we focused on phosphinoth-
ioformamide ligands,6 prepared by reaction of isothiocyanates and
diphenylphosphine (Scheme 1), since they can promote selective
coordination to gold(I) via the phosphorus atom, but in the vicinity
of other donor centres, leading to new and interesting structural
arrangements, which are also influenced by the ability of Au(I) to
promote aurophilic interactions.
The use of different alkyl or aryl isothiocyanates as starting ma-
terials permits, in principle, the preparation of new phosphinoth-
Scheme 1 General synthesis of phosphinothioformamide ligands and
mechanism of addition (A) and intramolecular aromatic nucleophilic
ioformamide ligands varying the substituents at nitrogen and/or
phosphorus sites, which leads to variations in their electronic
properties and, hence, in their coordination abilities. In this sense,
substitution (B) for the formation of the phosphinobenzothiazole ligand.
= =
we thought that the use of the isothiocyanate C6F5–N C S as
duces a phosphinotetrafluorobenzothiazole ligand in quantitative
yield by initial formation of the desired phosphinothioformamide
ligand (see above) and a subsequent secondary transformation
consisting of an intramolecular nucleophilic substitution of flu-
orine leading to the thiazole ring (Scheme 1). This result seems
to be favoured by the characteristics of the pentafluorophenyl
ring, since the electronegativity of fluorine favours nucleophilic
attack on the electrophilic carbon centre and at the same time
fluorine has been reported to be a good leaving atom. This
type of perfluorobenzothiazole moiety has been reported as a
secondary product in the addition reaction of thiourea to C6F5–
starting material would lead to a new type of phosphinothiofor-
mamide ligand with different donor properties compared to the
already reported with Me- or Ph-substituents, taking into account
the higher electron accepting properties of the polyfluoroaromatic
= =
ring. Nevertheless, the addition of PPh2H to C6F5–N C S pro-
aDepartamento de Qu´ımica, Universidad de La Rioja, Grupo de S´ıntesis
Qu´ımica de La Rioja, UA-CSIC. Complejo Cient´ıfico-Tecnolo´gico, 26004,
Logron˜o, Spain. E-mail: eduardo.fernandez@dq.unirioja.es
bDepartamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de
Arago´n, Universidad de Zaragoza-CSIC, 50009, Zaragoza, Spain. E-mail:
alaguna@posta.unizar.es; Fax: +34 976 761187; Tel: +34 976 761185
=
N CClR (R = C6H5, C6F5) leading to aryl substituted perflu-
† Dedicated to Professor Antonio Garcia on the occasion of his 65th
birthday.
orobenzothiazoles following a similar addition plus intramolec-
ular nucleophilic aromatic substitution mechanism.7 Also, the
intramolecular cyclation of N-pentafluorophenylthioamides leads
to perfluorobenzothiazole units.8
‡ Electronic supplementary information (ESI) available: NMR for 1 (Fig.
S1); TDDFT excitations and MOs for 1a and 3a (Fig. S2–S5); population
analysis (Tables S1–S2). See DOI: 10.1039/b517728f
3672 | Dalton Trans., 2006, 3672–3677
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Results and discussion
The ligand diphenylphosphinotetrafluorobenzothiazole Ph2P-
(CNS)(C6F4) 1 is synthesized by refluxing in toluene an equimolec-
ular mixture of diphenylphosphine and pentafluorophenylisothio-
cyanate under an argon atmosphere. The control of the reaction
1
through 31P{ H}, 19F and 1H NMR spectroscopy and mass
spectrometry allows us to gain insight about the mechanism of
formation of this new ligand. Thus, for instance, after three hours
1
of reaction three species are observed in the 31P{ H} spectrum,
which correspond to the starting Ph2PH, the final benzothiazole 1
and a signal at 21 ppm that can be assigned to the phosphinoth-
ioformamide ligand C6F5–N(H)C(S)PPh2. The presence of this
derivative is confirmed by the 19F and 1H NMR spectra, since in
the former three additional signals to those of the starting material
and the final product at −142.61, −153.43 and −161.62 ppm,
corresponding to the pentaflourophenyl group, are observed; and
Fig. 2 The molecule of complex 3 in the crystal showing the numbering
scheme. Hydrogen atoms have been omitted for clarity.
1
the N–H proton appears at 8.12 ppm in its H NMR spectrum.
Also, the mass spectrum displays the corresponding peak at
m/z = 412 (100%) [C6F5–N(H)C(S)PPh2 + H]+. At t = 0 the
◦
˚
Table 1 Selected bond lengths [A] and angles [ ] for complex 2
1
31P{ H} NMR spectrum displays the signals corresponding to
the free diphenylphosphine and the dithioformamide intermediate
and after 6 hours the only product is the benzothiazole ligand.
These data support the mechanism of addition and subsequent
intramolecular nucleophilic aromatic substitution by initial for-
mation of the dithioformamide species.
The ligand Ph2P(CNS)(C6F4) reacts with gold(I) starting mate-
rials such as [AuCl(tht)] or [Au(C6F5)(tht)] (tht = tetrahydrothio-
phene) in a 1 : 1 molar ratio, leading to compounds of
stoichiometry [AuCl{Ph2P(CNS)(C6F4)}] 2 or [Au(C6F5){Ph2P-
(CNS)(C6F4)}] 3, respectively, by displacement of the labile ligand
tht. All physical and spectroscopic properties are in accordance
with the proposed stoichiometries and both crystal structures have
been established by X-ray diffraction studies.
Au–P
Au–Cl
P–C(21)
P–C(31)
P–C(1)
2.2252(12)
2.2759(13)
1.807(5)
1.808(5)
1.817(5)
C(1)–N
C(1)–S
S–C(11)
N–C(12)
1.302(6)
1.753(5)
1.729(5)
1.381(6)
P–Au–Cl
N–C(1)–S
N–C(1)–P
177.87(5)
116.6(3)
124.7(4)
S–C(1)–P
C(11)–S–C(1)
C(1)–N–C(12)
118.7(3)
88.3(2)
109.7(4)
◦
˚
Table 2 Selected bond lengths [A] and angles [ ] for complex 3
Au–C(41)
Au–P
P–C(31)
P–C(21)
P–C(1)
2.054(3)
2.2798(8)
1.812(4)
1.813(3)
1.836(4)
175.59(10)
116.4(3)
125.9(3)
C(1)–N
C(1)–S
1.299(4)
1.757(3)
1.382(4)
1.730(3)
N–C(11)
S–C(12)
By layering a dichloromethane solution of 2 with diethyl ether
or by slow evaporation of a CDCl3 solution of 3, single crystals
suitable for X-ray diffraction studies were obtained. Fig. 1 and 2
show the molecular structures and Tables 1 and 2 contain selected
C(41)–Au–P
N–C(1)–S
N–C(1)–P
S–C(1)–P
C(1)–N–C(11)
C(12)–S–C(1)
117.49(18)
110.3(3)
88.49(16)
bond distances and angles for 2 and 3, respectively. The crystal
structures consist of mononuclear [AuX{Ph2P(CNS)(C6F4)}] (X =
Cl (2), C6F5 (3)) units, with the gold(I) centre linearly coordinated
to Cl (2) or C6F5 (3) and to the phosphorus atom of the
benzothiazolephosphine ligand with a maximum deviation from
linearity of 4.41◦ in 3.
˚
The Au–P distances of 2.2252(12) (2) or 2.2798(8) A (3) are very
close to those observed for other related complexes containing the
fragment Cl–Au–P or C6F5–Au–P,6a,9 such as [Mo(CO)4{(PPh2)2-
9a
˚
CHPPh2}AuCl] (2.225(2) A),
[Mo(CO)4{(PPh2CH2)2CMe-
9b
˚
(CH2PPh2)}AuCl] (2.232(2) A) and [AuCl{Ph2PC(S)N(H)Me}]
6a
˚
(2.2254(7) A)
or [Mo(CO)4{(PPh2)2CHPPh2}Au(C6F5)]
[NBu4] [Mo(CO)4{(PPh2)2CPPh2}Au(C6F5)]
9a
˚
(2.274(2) A),
9a
˚
(2.283(2) A) and [Au2(C6F5)2{Ph2PC(S)N(H)Me}]2 (2.270(2)–
6a
˚
2.316(2) A), respectively, and show a higher trans influence of
the C6F5 group when compared to the chlorine atom.
Regarding the Au–Cl and Au–C bond lengths, of 2.2759(13) (2)
˚
and 2.054(3) A (3), respectively, they are also similar to those found
˚
in the compounds mentioned above (from 2.275(1) to 2.2866(8) A
Fig. 1 The molecule of complex 2 in the crystal showing the numbering
scheme. Hydrogen atoms have been omitted for clarity.
6a,9
˚
for Au–Cl and from 2.041(8) to 2.074(7) A for Au–C).
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Table 3 Spectroscopic and photophysical properties of 1–3
Complex
Medium (T/K)
kabs b/nm (e/mol−1 dm3 cm−1
)
kem(kexc)/nm [s/ls]
1
CH2Cl2 (298)
Solid (298)
Solid (77)
233 (4.28 × 104), 268 (2.38 × 104), 297 (3.60 × 104)
Non-emissive
510 (350) [10.6]
555 (343)
506 (320)
Non-emissive
473 (340) [152.6, 9.1]
461, 488, 516 (330)
451, 479, 511 (310)
Non-emissive
484 (350) [44.8, 13.4]
453, 481, 511 (342)
445, 474, 507 (310)
Glassa (77)
CH2Cl2 (298)
Solid (298)
Solid (77)
2
3
239 (4.86 × 104), 278 (2.26 × 104)
Glassa (77)
CH2Cl2 (298)
Solid (298)
Solid (77)
242 (6.52 × 104), 278 (3.34 × 104)
Glassa (77)
a EtOH/MeOH/CH2Cl2 (v/v/v, 8 : 2 : 1). b 5 × 10−5 M in CH2Cl2.
The bond lengths and angles within the thiazole ring compare
well with those found in other derivatives containing this group.10
Finally, both crystal structures also show intramolecular
region and, in addition, the ligand displays a lower energy band at
297 nm. The fact that the higher energy bands are similar for the
complexes and the ligand suggests intraligand 1IL (p → p*)(N–C)
transitions. Similar assignments in related benzothiazole ligands
have been reported previously.12 The band placed at lower energy
is tentatively assigned to a 1IL (n → p*) transition, which is
absent in the case of the gold complexes. Theoretical TD-DFT
calculations (see below) agree with this assumption. The excitation
peaks in the solid state are red shifted from the absorption bands
seen in solution suggesting spin-forbidden transitions. Also, the
lifetime measurements, in the solid state at room temperature, in
the microsecond range are consistent with this and, therefore, with
phosphorescence. The presence of gold in the complexes seems to
affect the luminescence increasing the intensity of the emission
and the lifetime of the excited states responsible for it.
˚
Au · · · S weak interactions of 3.4603(12) (2) or 3.3409(9) A (3),
which are of the same order of magnitude as the Au–S distances
observed in [Au2(Ph2P(CH2)6PPh2)6({C6H3(NH2)}{CNS}S)2] or
11
˚
[Au(P(CH2CH2CN)3)({C6H3(NH2)}{CNS}S)2] (3.28–3.57 A).
On the other hand, benzothiazole ligands are known to display
interesting photophysical properties improving the photostability
and emission intensity in conjugated systems as well as in the
complexes that contain them.12,13 Also, the presence of gold(I) in
the complexes should enhance the phosphorescence and, on the
other hand, fluorinated materials facilitate thin film fabrication
and offer thermal and oxidative stability.14–20 These are important
characteristics in the products used as emitting materials for light-
emitting devices (LED’s).
The emission bands for complexes 2 and 3 at 77 K in the
solid state and in an alcohol glass appear at similar energies and
with similar structures. Both display peaks in the ranges 445–461,
474–488 and 507–516 nm with tailing extending to ca. 600 nm,
nevertheless, in the case of ligand 1 the emission is broad and
unstructured even at low temperatures (see Fig. 3) The spacing
between peaks in the case of complexes 2 and 3 is about 1400 cm−1,
which is assigned to a vibrational mode of the heterocyclic ring
of the ligand, which also appear in their IR spectra. These facts
are indicative of different origins of the excited states in the ligand
and in the gold complexes. Thus, while the anionic ligand bonded
to gold (Cl 2, C6F5 3) seems not to affect the transitions, since one
would expect a bigger difference in the energy of the emissions for
both complexes, the presence of the gold centre must influence the
electronic structure of the ligand, because the emission appears at
different energy and does not show any structure. Therefore, what
seems likely is that in the case of the free ligand the origin of the
transition is the free electron pair of the unsaturated phosphorous
atom giving rise to a n(P) → p*(heterocyclic ring) excited state,
while the coordination of this phosphorus to the gold centre leads
to a gold-perturbed p → p*(heterocyclic ring) excited states in the
complexes 2 and 3, respectively.
The benzothiazole ligand 1 as well as the complexes 2 and 3
exhibit bright luminescence in the solid state at room temperature
and at 77 K and in glass media at 77 K (see Fig. 3 and Table 3),
but neither in deoxygenated dichloromethane nor in acetonitrile
solutions. The absorption spectra for the three compounds in
CH2Cl2 show similar bands at high energy for the ligand and
both complexes (e of the order 104 dm3 mol−1 cm−1) in the UV
These results are supported by the analyses of the molecular
orbitals and the theoretical excitations obtained by DFT and TD-
DFT calculations, respectively. Taking into account the accessible
computational costs we have used as a theoretical model system
3a, the molecular geometry of which has been obtained through
Fig. 3 Emission spectra of 1 (solid line) and 3 (dashed line) in alcohol
glass at 77 K.
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X-ray diffraction analysis for complex 3, that represents the
photophysical behaviour of complexes 2 and 3 and a fully DFT-
B3LYP optimized model system 1a that represents ligand 1.
In order to reproduce theoretically the absorption spectra of
ligand 1 and complex 3 we carried out time-dependent DFT
calculations of the first few singlet excitations for models 1a and
3a (see ESI‡ for 1a). The obtained results confirm the above
mentioned character of the spin allowed transitions observed
experimentally. Thus, for the ligand 1 the character of the occupied
orbitals involved in these excitations agree well with a n(P)
character for the low energy band at 297 nm and a p character for
the high energy bands at 233 and 268 nm, meanwhile for complex
3 a p character (slightly gold-perturbed) for the bands at 242 and
278 nm is observed. The p* character for the empty orbitals is also
confirmed in both cases. Moreover, the energy of the oscillator
strengths for the predicted theoretical excitations for models 1a
and 3a clearly matches the experimental ones (see Fig. 4 for model
3a).
Fig. 5 Experimental excitation spectra of 1 (black) and 3 (red) and first
triplet excitation (only energy positions) for models 1a (black) and 3a (red).
of the C6F4(CNS) heterocyclic ring at 399 nm (experimental:
388 nm).
Experimental
General
The compounds [AuCl(tht)]21 and [Au(C6F5)(tht)]22 were prepared
by literature methods. The starting materials PPh2H and C6F5NCS
were purchased from Sigma-Aldrich and used as received.
Instrumentation
Infrared spectra were recorded in the 4000–200 cm−1 range on
a Perkin-Elmer FT-IR Spectrum 1000 spectrophotometer, using
Nujol mulls between polyethylene sheets. C, H, N, S analyses
were carried out with a C.E. Instrument EA-1110 CHNS-O
microanalyser. Mass spectra were recorded on a HP-5989B
Mass Spectrometer API-Electrospray with interface 59987A. 1H,
Fig. 4 Absorption spectrum (solid line) of 3 in 5 × 10−5 M CH2Cl2
solution, first few theoretical singlet excitations of model 3a (bars) and
experimental excitation spectrum of 3 (dashed line) in the solid state at
room temperature.
1
19F, and 31P{ H} NMR spectra were recorded on a Bruker
ARX 300 in CDCl3 or d8-toluene solutions. Chemical shifts are
quoted relative to SiMe4 (1H external), CFCl3 (19F external) and
H3PO4 (85%) (31P, external). Absorption spectra in solution were
registered on a Hewlett Packard 8453 Diode Array UV-visible
spectrophotometer. Excitation and emission spectra as well as
lifetime measurements were recorded with a Jobin-Yvon Horiba
Fluorolog 3–22 Tau-3 spectrofluorimeter.
As we have mentioned before, the experimental excitation peaks
responsible for the emissions of 1–3 in the solid state are red shifted
from the absorption bands suggesting spin-forbidden transitions.
In this sense, we have used TD-DFT calculations to predict the
energy of the lowest triplet excitation for each case that could
be assigned to the experimental energy excitation that leads to
phosphorescence (Fig. 5).
Synthesis
From the photophysical measurements at low temperature in the
solid state and in glassy solution a different behaviour is observed
for the ligand 1 and for the complexes 2 and 3. The unstructured
emission band observed for the ligand could be assigned to the
theoretical triplet transition between the 99a and 100a orbitals
(see Fig. 5) at 352 nm (experimental: 350 nm) leading to a n(P) →
p* transition as predicted experimentally. On the other hand the
structured emission for 3, consistent with starting orbitals located
at the heterocyclic ring, is in agreement with the theoretical triplet
transition that, upon coordination of the P atom to the gold
fragment, takes place between p (147a) and p* (150a) orbitals
Ph2P(CNS)(C6F4) (1). To a solution of (C6F5)NCS (0.6 mL,
3.54 mmol) in 30 mL of toluene was added Ph2PH (0.5 mL,
3.54 mmol) under an Argon atmosphere. The resulting yellow
solution was heated under reflux for 6 hours and then cooled to
room temperature. The solvent was removed in vacuo, and the
yellow oily residue was treated with ethanol. Then, the solution
was cooled in the refrigerator until yellow crystals of 1 appeared.
Yield: 0.65 g (46.9%). Mass spectrum: [M + H]+ at m/z = 392.
Anal. Calcd. for C19H10F4NPS·0.5EtOH: C, 57.98; H, 3.16; N,
3.39; S, 7.73. Found C, 58.44; H, 3.17; N, 3.57; S, 7.90%. IR:
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1
1337 cm−1 (heterocyclic ring). 31P{ H} NMR(CDCl3) d: −6.35 (s).
and dihedral angles frozen, single-point DFT calculations were
performed on model 3a. In both the ground-state calculations and
the subsequent calculations of the electronic excitation spectra,
the B3LYP functional24 as implemented in TURBOMOLE25
was used. The excitation energies were obtained at the density
functional level by using the time-dependent perturbation theory
approach (TD-DFT),26–30 which is a DFT generalization of
the Hartree–Fock linear response (HF-LR) or random-phase
approximation (RPA) method.31 In all calculations, the Karlsruhe
split-valence quality basis sets32 augmented with polarization
functions33 were used (SVP). The Stuttgart effective core potential
in TURBOMOLE was used for Au.34 Calculations were performed
without any assumption of symmetry for 1a and 3a.
19F NMR (CDCl3) d: −137.63 [m, 1F, o-S], −146.56 [m, 1F, o-N],
1
−157.72 [m, 1F, p-S], −158.68 [m, 1F, p-N] H NMR(CDCl3) d:
7.56–7.41 [m, aromatic protons].
[AuCl{Ph2P(CNS)(C6F4)}] (2). To a dichloromethane solu-
tion (20 mL) of [AuCl(tht)] (0.08 g, 0.255 mmol) was added
C6F4NCSPPh2 (0.1 g, 0.255 mmol) and after 30 minutes of stirring
the solvent was evaporated to ca. 5 mL. Addition of n-hexane
(20 mL) led to precipitation of complex 2 as a white solid. Yield:
0.14 g (89.8%). Mass spectrum: [M − Cl]+ at m/z = 588.6.
Anal. Calcd for C19H10AuClF4NPS: C, 36.59; H, 1.62; N, 2.24;
S, 5.14. Found C, 36.45; H, 1.65; N, 2.31; S, 4.95%. IR: 1335 cm−1
(heterocyclic ring), 342 cm−1 (Au–Cl). 31P{ H} NMR(CDCl3) d:
1
23.33 (s). 19F NMR (CDCl3) d: −136.27 [m, 1F, o-S], −144.22
[m, 1F, o-N], −154.36 [m, 1F, p-S], −155.05 [m, 1F, p-N] 1H
NMR(CDCl3) d: 7.88–7.25 [m, aromatic protons].
Acknowledgements
The D.G.I.(MEC)/FEDER (CTQ2004-05495) project is acknowl-
edged for financial support. M. Monge thanks the MEC-
Universidad de La Rioja for his research contract “Ramo´n y
Cajal”. M. Montiel thanks the C.A.R. for a grant. Dr A. Avenoza
is acknowledged for fruitful discussions.
¯
Crystal data for 2. C19H10AuClF4NPS, triclinic, P1, a =
◦
˚
8.3342(3), b = 10.2580(3), c = 11.4515(4) A, a = 97.223(1) ,
◦
◦
3
˚
b = 96.787(1) , c = 97.010(1) , V = 955.08(6) A , Z = 2,
l = 8.077 mm−1, 13716 reflections, 2hmax 55.98◦, 4450 unique
(Rint = 0.0630), R = 0.0354, Rw = 0.0864 for 293 parameters,
−3
˚
76 restrictions, S = 1.025, max. Dq = 2.580 e A .
References
[Au(C6F5){Ph2P(CNS)(C6F4)}] (3). To a dichloromethane so-
lution (20 mL) of [Au(C6F5)(tht)] (0.23 g, 0.51 mmol) was added
C6F4NCSPPh2 (0.2 g, 0.51 mmol) and after 1 hour of stirring the
solvent was evaporated to dryness to give a white solid 3. Yield:
0.34 g (78.8%). Mass spectrum: [AuL2]+ (L = C6F4NCSPPh2 1)
at m/z = 979.0 Anal. Calcd for C25H10AuF9NPS: C, 39.75; H,
1.33; N, 1.85; S, 4.24. Found C, 40.07; H, 1.35; N, 1.81; S, 4.06%.
IR: 1356 cm−1 (heterocyclic ring), 1496, 955, 793 cm−1 (Au–C6F5).
1 W. S. Rapson and T. Groenewald, Gold Usage, Academic Press,
London, 1978.
2 P. J. Sadler, Gold Bull., 1976, 9, 110.
3 K. C. Dash and H. Schmidbaur, in Metal Ions in Biological Systems,
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4 A. Ulman, Chem. Rev., 1996, 96, 1533 and references therein.
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6 (a) O. Crespo, E. J. Ferna´ndez, P. G. Jones, A. Laguna, J. M. Lo´pez-de-
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1
31P{ H} NMR(CDCl3) d: 32.24 (s). 19F NMR (CDCl3) d: −136.45
[m, 1F, o-S, C6F4], −144.58 [m, 1F, o-N, C6F4], −155.04 [m, 1F,
p-S, C6F4], −155.53 [m, 1F, p-N, C6F4]; −116.24 (m, 2F, Fo, C6F5),
−157.45 (t, 1F, Fp, C6F5, J(Fp–Fm) = 20.0 Hz), −162.12 (m, 2F,
Fm, C6F5). 1H NMR(CDCl3) d: 7.95–7.25 [m, aromatic protons].
Crystal data for 3. C25H10AuF9NPS, monoclinic, P21/c, a =
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◦
˚
8.5376(2), b = 18.7340(5), c = 14.7669(4) A, b = 90.757(1) , V =
3
−1
˚
2361.66(11) A , Z = 4, l = 6.473 mm , 18493 reflections, 2hmax
55.70◦, 5465 unique (Rint = 0.0423), R = 0.0265, Rw = 0.0583 for
383 parameters, 123 restrictions, S = 1.040, max. Dq = 1.339 e
−3
˚
A .
Crystal data for 2 and 3 were measured at −100 ◦C using
a Nonius KappaCCD diffractometer, Mo-Ka radiation, x and
φ-scans. The structures were solved by direct methods and
refined anisotropically on F2.23 Hydrogen atoms were located
in the Fourier map and refined without restrictions. Absorption
correction: multi-scan.
15 M. A. Omary, R. M. Kassab, M. R. Haneline, O. Elbjeirami and F. P.
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For crystallographic data in CIF or other electronic format see
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Computational details for TD-DFT calculations
The molecular structures used in the theoretical studies on
Ph2P(CNS)(C6F4) 1a and [Au(C6F5){Ph2P(CNS)(C6F4)}] 3a
were taken from the X-ray diffraction data for [Au(C6F5)-
{Ph2P(CNS)(C6F4)}] 3, respectively. For model 1a a full geometry
optimization was carried out. Keeping all distances, angles
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3676 | Dalton Trans., 2006, 3672–3677
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