Synthesis, structures and anti-malaria activity of some gold(i) phosphine complexes containing seleno- and thiosemicarbazonato ligands

Article abstract of DOI:10.1039/c1dt10885a

A series of both mono- and dinuclear gold(i) phosphine complexes containing monoanionic seleno- and thiosemicarbazones as ligands were prepared and fully characterized by spectroscopic methods and, in some cases, by single crystal X-ray diffraction. The in vitro anti-malaria activity of some of these compounds was investigated in chloroquine sensitive strains of Plasmodium falciparum. The IC₅₀ results show that the sulfur containing compounds exhibit activity similar to that of chloroquine, whilst the selenium derivatives display only moderate anti-malaria activity.

Full text of DOI:10.1039/c1dt10885a

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PAPER
Synthesis, structures and anti-malaria activity of some gold(I) phosphine
complexes containing seleno- and thiosemicarbazonato ligands†
Anja Molter,a Jo¨rg Rust,b Christian W. Lehmann,b Ganesh Deepa,c Peter Chiba*c and Fabian Mohr*a
Received 10th May 2011, Accepted 15th July 2011
DOI: 10.1039/c1dt10885a
A series of both mono- and dinuclear gold(I) phosphine complexes containing monoanionic seleno-
and thiosemicarbazones as ligands were prepared and fully characterized by spectroscopic methods
and, in some cases, by single crystal X-ray diffraction. The in vitro anti-malaria activity of some of these
compounds was investigated in chloroquine sensitive strains of Plasmodium falciparum. The IC50 results
show that the sulfur containing compounds exhibit activity similar to that of chloroquine, whilst the
selenium derivatives display only moderate anti-malaria activity.
especially 2-acetylpyridyl functionalized selenosemicarbazones as
well as their sulfur analogues have been investigated for their anti-
Introduction
malaria activity in the 1980’s by Klayman.24–26 In continuation of
our exploration of gold–selenium chemistry27,28 and our general
interest in biologically active metal complexes,16,29–32 we decided
to combine selenium and sulfur ligands with known anti-malaria
activity with a gold phosphine unit. We aimed at studying the
chemistry of these compounds and assessing their anti-malaria
activity, the results are presented herein.
Although the chemistry of sulfur containing gold compounds is a
well established field, scientists worldwide are still making new dis-
coveries and are developing new applications for these compounds.
Efforts over the past have focused mainly on photophysical
properties, applications in medicine as well as the supramolecular
chemistry of these compounds.1,2 Several anti-arthritis drugs based
on gold–sulfur compounds including the well-known Auranofin
(trade name: Ridaura) have been on the market for more
than 30 years.3–5 In marked contrast, the chemistry of selenium
containing gold compounds has been much less studied.6
Results and discussion
Malaria is a potentially lethal tropical disease caused by
the parasite Plasmodium falciparum, which is transferred to
humans through the bite of female anopheles mosquitoes. The
local and also global economic impact of this disease, which
affects more than 243 million people annually (approximately
one death every 30 s), is significant.7–10,11 The most successful
and widely used anti-malaria drug, chloroquine, is today however
virtually ineffective due to development of parasite resistance.12
Thus, although there is urgent need for new anti-malaria drugs,
research progress is slow and, since malaria is a disease of the
poor where little return on investment can be expected, the
multinational drug companies are concentrating research efforts
more on drugs against obesity and hair loss. Some groups have
recently examined metal complexes as a potentially new class
of anti-malaria drugs. Examples containing gold,13–16 platinum,17
ruthenium,18–20 rhodium14 and ferrocene derivatives, in particular
ferroquine21–23 have been reported. Organoselenium compounds,
Selenosemicarbazones HSe1 and HSe2 as well as the thiosemicar-
bazones HS1, HS2 and HS3 were prepared according to literature
procedures. In solution, three isomers Z, E and EZ (Scheme 1)
can be observed by NMR spectroscopy. In the solid-state however,
the EZ isomers of HSe1 and HS1 are found. These results are
in agreement with data for HSe2 and HS2 which were reported
recently by Kowol et al.33 In the case of HS3, only the Z and E
isomers can be observed by NMR spectroscopy.
The mono- and dinuclear phosphine gold(I) complexes, [AuLP]
and [Au2L2(P–P)], containing deprotonated selenosemicarbazones
HSe1 or HSe2, or thiosemicarbazones HS1, HS2 or HS3 as
ligands were prepared in good yields from the reaction of
the appropriate phosphine gold(I) chlorides with the seleno- or
thiosemicarbazones in the presence of base as colorless or yellow
solids (Scheme 2). In the solid state the compounds appear stable
indefinitely. However, most of the selenium derivatives decompose
over a period of 12–24 h in solution.
aFachbereich C - Anorganische Chemie, Bergische Universita¨t Wuppertal,
42119, Wuppertal, Germany. E-mail: fmohr@uni-wuppertal.de
The new gold complexes were fully characterized by spectro-
scopic methods. In all cases, the deprotonation of the seleno- or
thiosemicarbazone unit was apparent from the absence of the N–
H signal in the H-NMR spectra. The 31P{ H}-NMR spectra of
the complexes show singlet resonances, which are shifted by ca. 2
to 11 ppm to the higher field compared to those of the phosphine
gold(I) chloride complexes. The signals of the selenium compounds
bMax-Planck-Institut fu¨r Kohlenforschung, 45470, Mu¨lheim an der Ruhr,
Germany (X-Ray crystallography)
1
1
cInstitute of Medical Chemistry, Medical University of Vienna, 1090, Vienna,
Austria. E-mail: peter.chiba@meduniwien.ac.at
† CCDC reference numbers 803631–803635, 833228. For crystallographic
data in CIF or other electronic format see DOI: 10.1039/c1dt10885a
9810 | Dalton Trans., 2011, 40, 9810–9820
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Scheme 1
Scheme 2
Fig. 1 Molecular structure of HS1 and HSe1. Ellipsoids are drawn at the 50% probability level. Hydrogen atoms shown as spheres with arbitrary radii.
generally exhibit slightly higher shifts in comparison to their sulfur
analogues. For the selenium derivatives 77Se NMR spectra could
be obtained in some cases, which show singlet resonances at ca.
30–50 ppm except the dppee complexes where the singlet appears
at about 80 ppm. For comparison, the 77Se NMR chemical shifts
for HSe1 and HSe2 are observed at 65 (EZ) and 328 (E, Z) and
at 83 (EZ) and 322 (E, Z) ppm, respectively. Based on the NMR
studies by Kowol et al., the higher field signals are those of the EZ-
isomer. It seems reasonable to compare the 77Se NMR signals of
the gold complexes with these, since the electron distribution in the
EZ-isomer resembles that in the complexes. A further diagnostic
feature is the 13C chemical shift of the carbon atom of the
C–E unit with partial double bond character, which experi-
ences an upfield shift upon coordination to the gold atom,
consistent with a change of bond order. While the signals of
the sulfur compounds are shifted about 10 to 15 ppm upfield,
those of the selenium counterparts are shifted 15 to 20 ppm
upfield due to the higher electron density of the selenium
atom. The proposed structures were confirmed by single crystal
X-ray diffraction studies of the 2-methylpiperidyl substituted
thio- and selenosemicarbazones HS1 and HS2, the mononu-
clear sulfur complexes [Au(S2)(PPh3)] and the dinuclear sulfur
and selenium compounds [Au2(S2)2(l-dppee)], [Au2(S3)2(l-dppb)]
and [Au2(Se1)2(l-dppf)]. The molecular structures are shown in
Fig. 1–5; important bond lengths and angles are collected in
Table 1.
Fig. 2 Molecular structure of complex [Au(S2)(PPh3)]. Ellipsoids are
drawn at the 50% probability level. Hydrogen atoms have been omitted for
clarity.
The thio- and selenosemicarbazones HS1 and HSe1 are
structurally very similar. Both contain a planar backbone due
˚
˚
to intramolecular hydrogen bonding (HS1: Npy ◊ ◊ ◊ H 2.24 A,
◦
˚
Npy ◊ ◊ ◊ (H)N 2.644 A, Npy ◊ ◊ ◊ H–N 106.9 , S ◊ ◊ ◊ H 2.32 A,
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Table 1 Important bond distances and angles of HS1, HSe1 and the gold complexes [Au(S2)(PPh3)], [Au2(S2)2(l-dppee)], [Au2(S3)2(l-dppb)] and
[Au2(Se1)2(l-dppf)]
HS1
HSe1
[Au(S2)(PPh3)]
[Au2(S2)2(m-dppee)]
[Au2(S3)2(m-dppb)]
[Au2(Se1)2(m-dppf)]
˚
Bond distances [A]
P–Au
Au–E
E–C
—
—
—
—
1.881(2)
1.344(3)
2.246(2)
2.312(2)
1.757(8)
1.309(10)
2.2507(7)
2.3119(7)
1.768(3)
1.315(4)
2.2519(8)
2.3135(8)
1.744(3)
1.282(4)
2.2633(6)
2.4194(2)
1.941(2)
1.306(3)
1.7158(14)
1.3628(17)
(E)C–N(N)
Bond and torsion angles [◦]
P–Au–E
Au–E–C
E–C–N(N)
E–C–N–N
N(py)–C–C–N
—
—
—
—
168.73(8)
104.5(3)
129.1(6)
10.0(10)
166.5(7)
169.91(3)
104.25(9)
128.3(3)
8.1(6)
172.09(3)
105.19(12)
132.0(3)
8.8(5)
173.429(15)
97.36(7)
126.2(2)
0.4(3)
124.49(10)
1.4(2)
0.8(2)
124.16(17)
0.9(3)
4.5(3)
164.4(4)
166.6(3)
171.7(2)
Fig. 3 Molecular structure of complex [Au2(S2)2(l-dppee)]. Ellipsoids are
drawn at the 50% probability level. Only the ipso carbon atoms of the Ph2P
groups are shown. Hydrogen atoms have been omitted for clarity.
Fig. 5 Molecular structure of complex [Au2(Se1)2(l-dppf)]. Ellipsoids are
drawn at the 50% probability level. Only the ipso carbon atoms of the Ph2P
groups are shown. Hydrogen atoms have been omitted for clarity.
and the pyridyl nitrogen atom. The significant degree of electron
delocalization in the molecule is apparent from the bond distances
(Table 1); in particular inducing single bond character to the CE
(E: S, Se) bond.
The structures of the gold complexes consist of the deprotonated
chalcogenosemicarbazone coordinating to the gold via the S
or Se atoms, respectively. The virtually linear (ca. 168–173◦)
coordination about the gold atoms is completed by the phosphine
ligand. The bond distance data (Table 2) show clearly that the C–
E bond distances in the complexes are lengthened between 0.028
Fig. 4 Molecular structure of complex [Au2(S3)2(l-dppb)]. Ellipsoids are
drawn at the 50% probability level. Hydrogen atoms have been omitted for
clarity.
◦
˚
˚
˚
˚
S ◊ ◊ ◊ (H)N 2.948 A, S ◊ ◊ ◊ H–N 117.0 ; HSe1: Npy ◊ ◊ ◊ H 2.26 A,
and 0.06 A in comparison to those in the free chalcogenosemi-
◦
˚
Npy ◊ ◊ ◊ (H)N 2.660(3) A, Npy ◊ ◊ ◊ H–N 107.2 , Se ◊ ◊ ◊ H 2.37 A,
Se ◊ ◊ ◊ (H)N 2.864(2) A, Se ◊ ◊ ◊ H–N 115.7 ) between the azome-
carbazones, illustrating the delocalization of its backbone. In the
◦
˚
S2 derivatives, the bond distance is lengthened by ca. 0.034 to
˚
˚
thine nitrogen atom to the hydrogen which bridges to the chalcogen
0.045 A while that of the Se1 derivative increases by about 0.06 A.
9812 | Dalton Trans., 2011, 40, 9810–9820
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Table 2 IC50 values of complexes [Au(Se1)(PPh3)], [Au(S1)(PPh3)],
[Au(Se2)(PPh3)] and [Au(S2)(PPh3)]
lines used and the determined LC50 values cannot be compared to
the data of our compounds.
Complex
IC50 [nM]
Conclusion
[Au(S1)(PPh3)]
[Au(Se1)(PPh3)]
[Au(S2)(PPh3)]
[Au(Se2)(PPh3)]
Chloroquine
10.7 1.44
60.5 4.45
7.06 0.78
135 13.4
8.84 2.13
We present here the preparation and characterization of a family
of gold(I) seleno- and thiosemicarbazonato complexes that show
promising anti-malaria activity. Further studies of this class of
compounds are ongoing in our laboratories.
This is further evidenced by the shortening of the C–N bond in
the E–C–N–N unit of the coordinated ligands by ca. 0.035 to
0.041 A. As can be seen from the torsion angles, the coordinated
Experimental section
˚
ligand remains almost completely planar, also due to extensive
electron delocalization. While the nitrogen atom of the pyridyl
ring is directed towards the azomethine nitrogen atom in the solid
state structure of the free ligand, it lies in the opposite direction
towards the methyl group in the gold complexes. Curiously, there
is an absence of intra- or intermolecular Au–Au contacts which
are often observed in gold(I) compounds, particularly in dinuclear
complexes. It is noteworthy that in the three structures the ligands
are oriented such that the imine nitrogen atom is directed towards
General
1H, 13C{ H}, 31P{ H} and 77Se NMR spectra were recorded on a
Bruker Avance ARX 400 (400 MHz) or a Bruker Avance III 600
(600 MHz) spectrometer. Chemical shifts are quoted relative to
external SiMe4 (1H, 13C), H3PO4 (31P) and KSeCN or Me2Se (77Se)
as specified below. Elemental analyses were performed by staff
of the micro-analytical laboratory of the University of Wuppertal.
The thiosemicarbazones HS1–HS336–38 and selenosemicarbazones
HSe1 and HSe224,26 were prepared as described in literature.
The phosphine gold chloride precursors were prepared from the
reaction of [AuCl(tht)] (tht = tetrahydrothiophene)39 with the
appropriate phosphines. All other chemicals and solvents (HPLC
or extra dry grade) were sourced commercially and used as
received.
HS1 has been reported previously, but incomplete NMR data
were provided. For comparison, we include the data here. The
compound exists in DMSO solution as a mixture of three isomers
EZ : E : Z in an approximate ratio of 0.8 : 1 : 0.2 as determined
from the integrals. Assignments are based on comparison with
literature data of HS2 and HSe2.33
1
1
˚
the gold atom with a distance of 2.7–2.8 A, suggestive of a weak
interaction.
To the best of our knowledge, these complexes represent the
first examples in which the multidentate chalcogenosemicarbazone
ligands coordinate to gold via the anionic chalcogen atom. The
only related structures known are two cationic gold(I) thiosemicar-
bazone complexes in which the thiosemicarbazones act as neutral
S-donor ligands (Chart 1).34,35
HS1: 1H NMR (600 MHz, DMSO-d6): d = 0.92 (d, J = 6.1 Hz,
9H, CHCH3E, Z, EZ), 1.06, 1.18 (br. s, 6H, CHax E, Z, EZ), 1.69
(m, 9H, CHeq, CHCH3 E, Z, EZ), 2.38, 2.60 (m, 9H, NCCH3 E,
Z, EZ), 2.99, 3.14 (br. s, 6H, NCHax E, Z, EZ), 4.97, 4.60 (m,
6H, NCHeq E, Z, EZ), 7.37 (m, 1H, H-5 py E), 7.49 (m, 1H, H-5
py EZ), 7.56 (dd, J = 7.3, 5.0 Hz, 1H, H-5 py Z), 7.78 (d, J =
7.9, 1H, H-3 py Z), 7.85, 7.97 (m, 4H, H-3 py E, EZ, H-4 py E,
EZ), 8.09 (dt, J = 7.9, 1.7 Hz, 1H, H-4 py Z), 8.59 (m, 1H, H-6
py E), 8.70 (m, 1H, H-6 py EZ), 8.75 (d, J = 4.2 Hz, 1H, H-6 py
Z), 9.64 (br. s, 1H, NH E), 14.81 (br. s, 1H, NH EZ), 15.18 (br. s,
Chart 1
1
1H, NH Z) ppm. 13C{ H} NMR (151 MHz, DMSO-d6): d = 12.2,
The in vitro anti-malaria activity of the triphenylphosphine gold
complexes with the ligands S1, S2, Se1 and Se2 were evaluated
in a strain of Plasmodium falciparum; the IC50 data are shown in
Table 2.
13.8 (NCCH3 E, Z, EZ), 21.6, 22.0 (CHCH3 E, Z, EZ), 30.7, 30.4
(CHCH3 E, Z, EZ), 34.0 (CH2 E, EZ), 33.6 (CH2 E, EZ), 49.4
(NCH2 Z), 49.4 (NCH2 E, EZ), 120.0 (C-3 py E), 122.3 (C-3 py
EZ), 124.4 (C-3 py Z), 124.0 (C-5 py E), 124.6 (C-5 py Z), 125.3
(C-5 py EZ), 136.7 (C-4 py E), 138.3 (C-4 py EZ), 138.8 (C-4 py
Z), 147.5, 149.9 (C-6 py EZ, Z), 148.7 (C-6 py E), 155.1 (CN E,
Z, EZ), 179.5 (CS Z), 182.0, 183.7 (CS E, EZ) ppm. X-ray quality
crystals were selected from the bulk sample.
HSe1 has been reported previously, but no NMR data was pro-
vided. For comparison we include the data here. The compound
exists in DMSO solution as a mixture of three isomers EZ : E : Z
in an approximate ratio of 1.0 : 0.4 : 0.1 as determined from the
integrals. Assignments are based on comparison with literature
data of HSe2.33
While the selenium derivatives [Au(Se1)(PPh3)] and
[Au(Se2)(PPh3)] show moderate activity, the sulfur compounds
display much higher activity, especially [Au(S2)(PPh3)] with an
IC50 value of 7.06 0.78, which is similar to that of chloroquine.
Although data from different strains are difficult to compare,
the gold complexes here show a higher activity in relation to
those previously reported by us and are significantly more active
than the chloroquine gold(I) phosphine complexes reported by
Navarro.13 The anti-malaria activity of the ligands themselves
have previously been reported by Klayman,24,36 however the cell
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HSe1: 1H NMR (400 MHz, DMSO-d6): d = 0.92 (d, J = 6.1 Hz,
3H, CHCH3EZ), 0.94 (m, 9H, CHCH3E, Z), 1.07 (m, 2H, CHax
EZ, CHax Z), 1.23 (q, J = 12.1 Hz, 2H, CHax E), 1.70 (m, 9H,
CHeq, CHCH3 E, Z, EZ), 2.37 (s, 3H, NCCH3 Z), 2.38 (s, 3H,
NCCH3 E), 3.03 (s, 3H, NCCH3 EZ), 3.03 (m, 2H, NCHax EZ),
3.23 (t, J = 12.4 Hz, 2H, NCHax E), 3.45 (m, 2H, NCHax Z), 4.32
(d, J = 13.2 Hz, 2H, NCHeq Z), 4.71 (d, J = 13.2 Hz, 2H, NCHeq
E), 5.05 (br. s, 2H, NCHeq EZ), 7.41 (m, 1H, H-5 py E), 7.55 (dd,
J = 7.3, 4.9, 5.1 Hz, 1H, H-5 py EZ), 7.58 (m, 1H, H-5 py Z), 7.81
(m, 1H, H-4 py Z), 7.85 (qd, J = 7.8, 1.6 Hz, 1H, H-4 py E), 7.91
(d, J = 8.1 Hz, 1H, H-3 py Z), 8.01 (dd, J = 7.8, 1.5 Hz, 1H, H-4
py EZ), 8.04 (d, J = 1.6 Hz, 1H, H-3 py E), 8.60 (d, J = 4.4 Hz, 1H,
H-6 py E), 8.76 (d, J = 4.1 Hz, 2H, H-6 py EZ, Z), 9.88 (br. s, 1H,
NH E), 14.71 (br. s, 1H, NH EZ), 15.21 (br. s, 1H, NH Z) ppm.
for C32H34AuN4PS (734.64 g mol-1): C 52.32, H 4.66, N 7.63, S
4.36; found: C 51.92, H 4.84, N 7.39, S 4.03.
[Au(S1)(PTA)] Workup method A: mustard yellow crystals.
1
Yield: 0.072 g (45%). H NMR (400 MHz, CD2Cl2): d = 0.95
(d, J = 6.1 Hz, 3H, CHCH3), 1.21 (m, J = 13.0, 4.0 Hz, 2H, CHax),
1.65 (m, 3H, CHeq, CHCH3), 2.51 (s, 3H, NCCH3), 2.93 (dt, J =
12.9, 1.8 Hz, 2H, NCHax), 3.66 (s, 6H, PCH2N), 4.30 (ABquart
,
2JH–H = 13.6 Hz, 6H, NCH2N), 4.86 (m, J = 13.2, 1.7 Hz, 2H,
NCHeq), 7.34 (ddd, J = 7.4, 4.8, 1.2 Hz, 1H, H-5 py), 7.81 (dt, J =
7.4, 1.8 Hz, 1H, H-4 py), 8.07 (dd, J = 8.0, 0.8 Hz, 1H, H-3 py),
1
8.67 (ddd, J = 4.8, 1.7, 0.9 Hz, 1H, H-6 py) ppm. 31P{ H} NMR
1
(162 MHz, CD2Cl2): d = -50.9 ppm. 13C{ H} NMR (101 MHz,
CD2Cl2): d = 15.6 (NCCH3), 22.2 (CHCH3), 32.2 (CHCH3), 34.9
1
(CH2), 48.8 (NCH2), 53.5 (d, JP–C = 20.0 Hz, PCH2N), 73.7 (d,
13C{ H} NMR (101 MHz, DMSO-d6): d = 12.3 (NCCH3 Z), 14.2
3JP–C = 7.7 Hz, NCH2N), 123.0 (C-3 py), 123.4 (C-5 py), 136.1
(C-4 py), 149.5 (C-6 py), 157.1 (N), 160.0 (CN), 173.5 (CS) ppm.
Elemental analysis calcd. (%) for C20H31AuN7PS · 1 H2O (647.53
g mol-1): C 37.10, H 5.14, N 15.14, S 4.95; found: C 36.96, H 5.40,
N 15.03, S 4.64
1
(NCCH3 EZ), 12.3 (NCCH3 E), 21.2 (CHCH3 E), 21.4 (CHCH3
EZ), 21.9 (CHCH3 Z), 30.0 (CHCH3 Z), 30.1 (CHCH3 E), 30.7
(CHCH3 EZ), 33.9 (CH2 E, Z, EZ), 52.7 (NCH2 E, EZ), 55.9
(NCH2 Z), 120.0 (C-3 py E), 122.6 (C-3 py EZ), 124.0 (C-5 py E),
124.4 (C-3 py Z), 124.6 (C-5 py Z), 125.5 (C-5 py EZ), 136.5 (C-4
py E), 138.1 (C-4 py EZ), 138.7 (C-4 py Z), 143.2 (CN), 147.5 (C-6
py Z), 147.9 (CN), 148.7 (C-6 py E), 149.9 (C-6 py EZ), 151.1 (CN
Z), 152.1 (CN E), 154.8 (CN EZ), 187.7 (CS Z), 180.5 (CS E),
182.0 (CS EZ) ppm. 77Se (114 MHz, DMSO-d6, Me2Se): d = 65
(EZ), 328 (E, Z) ppm. X-ray quality crystals were selected from
the bulk sample.
[Au2(S1)2(l-dppe)] Workup method B, washed with diethyl
1
ether: light yellow crystals. Yield: 0.054 g (69%). H NMR (400
MHz, CDCl3): d = 0.97 (d, J = 6.1 Hz, 6H, CHCH3), 1.30 (qd,
J = 11.5 3.6 Hz, 4H, CHax), 1.69 (m, 6H, CHeq, CHCH3), 2.09
(s, 4H, PCH2), 2.56 (s, 6H, NCCH3), 3.02 (t, J = 12.0 Hz, 4H,
NCHax), 5.02 (d, J = 13.0 Hz, 4H, NCHeq), 6.40 (t, J = 7.4 Hz,
2H, H-4 py), 6.63 (t, J = 6.7 Hz, 2H, H-5 py), 7.33 (m, 16H, o-
PPh2, m-PPh2), 7.39 (m, 4H, p-PPh2), 7.97 (d, J = 7.9 Hz, 2H, H-3
1
py), 8.23 (d, J = 4.1 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162
1
Preparation of the gold thiosemicarbazone complexes. To a
solution of the appropriate thiosemicarbazones (HS1, HS2 or
HS3) in MeOH (10 mL) was added sodium methoxide (1.2
equivalents) and the mixture was stirred for 15 min. Subsequently,
the solid phosphine gold chloride (0.9 equivalents) was added
and the mixture was stirred at room temperature overnight with
protection from light. Two workup methods were then used:
A) When a suspension formed the solid was isolated by
filtration, washed with a small amount of MeOH, water and Et2O
and subsequently dried in air.
MHz, CDCl3): d = 35.5 ppm. 13C{ H} NMR (101 MHz, CDCl3):
d = 15.7 (NCCH3), 21.9 (CHCH3), 24.5 (PCH2), 31.7 (CHCH3),
34.3 (CH2), 48.2 (NCH2), 122.1 (C-5 py), 122.2 (C-3 py), 129.1
(ABX-t, m-PPh2), 129.9 (ABX-t, i-PPh2), 131.4 (p-PPh2), 133.1
(ABX-t, o-PPh2), 134.8 (C-4 py), 148.4 (C-6 py), 157.3 (CN),
158.3 (CN), 172.6 (CS) ppm. Elemental analysis calcd. (%) for
C54H62Au2N8P2S2 (1343.13 g mol-1): C 48.29, H 4.65, N 8.34, S
4.77; found: C 47.67, H 4.91, N 8.00, S 4.49.
[Au2(S1)2(l-dppee)] Workup method A: yellow crystals. Yield:
1
0.053 g (68%). H NMR (400 MHz, CDCl3): d = 0.97 (d, J =
B) When a solution formed, the mixture was evaporated to
dryness and the residue was dissolved in dichloromethane and
passed through celite. The solution was concentrated and the
products precipitated upon addition of a suitable solvent such
as diethyl ether, hexane or pentane. The solids were isolated by
filtration and subsequently dried in air.
56.0 Hz, 6H, CHCH3), 1.29 (m, 4H, CHax), 1.72 (m, 6H, CHeq,
CHCH3), 2.60 (s, 6H, NCCH3), 3.04 (t, J = 12.6 Hz, 4H, NCHax),
5.06 (d, J = 12.6 Hz, 4H, NCHeq), 5.56 (m, 2H, PCH), 6.67 (dt, J =
7.6, 1.4 Hz, 2H, H-4 py), 6.88 (dt, J = 5.1 Hz, 2H, H-5 py), 7.24 (m,
8H, m-PPh2), 7.33 (m, 12H, o-PPh2, p-PPh2), 8.13 (dd, J = 7.9 Hz,
1
2H, H-3 py), 8.44 (dd, J = 3.5 Hz, 2H, H-6 py) ppm. 31P{ H}
1
[Au(S1)(PPh3)] Workup method A: light yellow crystals. Yield:
NMR (162 MHz, CDCl3): d = 24.5 ppm. 13C{ H} NMR (101
1
0.063 g (42%). H NMR (400 MHz, CD2Cl2): d = 0.96 (d, J =
MHz, CDCl3): d = 14.7 (NCCH3), 22.0 (CHCH3), 31.7 (CHCH3),
34.5 (CH2), 48.3 (NCH2), 121.8 (C-5 py), 122.8 (C-3 py), 129.2
(ABX-t, m-PPh2), 129.5 (ABX-t, i-PPh2), 131.2 (p-PPh2), 133.9
(ABX-t, o-PPh2), 134.9 (C-4 py), 137.6 (m, PCH), 147.9 (C-6 py),
155.6 (CN), 158.8 (CN), 172.7 (CS) ppm. Elemental analysis calcd.
(%) for C54H60Au2N8P2S2 (1341.12 g mol-1): C 48.36, H 4.51, N
8.36, S 4.78; found: C 47.81, H 4.30, N 8.43, S 4.30.
6.1 Hz, 3H, CHCH3), 1.23 (qd, J = 11.4, 2.6 Hz, 2H, CHax), 1.67
(m, 3H, CHeq, CHCH3), 2.53 (s, 3H, NCCH3), 2.96 (dt, J = 12.7,
1.9 Hz, 2H, NCHax), 4.95 (d, J = 13.2 Hz, 2H, NCHeq), 6.41 (dt,
J = 7.9, 1.6 Hz, 1H, H-4 py), 6.62 (ddd, J = 7.3, 4.9, 1.0 Hz,
1H, H-5 py), 7.25 (m, 6H, m-PPh3), 7.35 (m, 6H, o-PPh3), 7.45
(m, 3H, p-PPh3), 8.15 (d, J = 7.9 Hz, 1H, H-3 py), 8.29 (d, J =
1
4.6 Hz, 1H, H-6 py) ppm. 31P{ H} NMR (162 MHz, CD2Cl2): d =
[Au2(S1)2(l-dppp)] Workup method A: yellow crystals. Yield:
1
1
37.6 ppm. 13C{ H} NMR (101 MHz, CD2Cl2): d = 15.0 (NCCH3),
0.020 g (26%). H NMR (400 MHz, CDCl3): d = 0.94 (d, J =
21.8 (CHCH3), 31.8 (CHCH3), 34.4 (CH2), 48.3 (NCH2), 122.1
5.8 Hz, 6H, CHCH3), 1.24 (m, 6H, CHax, PCH2CH2), 1.68 (m,
6H, CHeq, CHCH3), 1.87 (m, 4H, PCH2), 2.52 (s, 6H, NCCH3),
3.00 (t, J = 12.4 Hz, 4H, NCHax), 5.32 (d, J = 12.9 Hz, 4H,
NCHeq), 6.38 (t, J = 7.6 Hz, 2H, H-4 py), 6.76 (m, 2H, H-5 py),
7.30–7.51 (m, 20H, PPh2), 7.99 (d, J = 7.8 Hz, 2H, H-3 py), 8.32
3
(C-3 py, C-5 py), 129.0 (d, JP–C = 11.3 Hz, m-PPh3), 130.7 (d,
4
1JP–C = 55.9 Hz, i-PPh3), 131.2 (d, JP–C = 2.4 Hz, p-PPh3), 134.1
(d, 2JP–C = 13.9 Hz, o-PPh3), 134.9 (C-4 py), 148.2 (C-6 py), 156.9
(CN), 158.2 (CN), 171.9 (CS) ppm. Elemental analysis calcd. (%)
9814 | Dalton Trans., 2011, 40, 9810–9820
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1
(d, J = 7.0, 3.3 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162 MHz,
H 4.27, N 8.55, S 4.67. Crystals suitable for X-ray diffraction were
grown by slow diffusion of hexane into a CH2Cl2 solution of the
complex.
CDCl3): d = 31.6 ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.5
1
1
(NCCH3), 21.9 (CHCH3), 27.6 (d, JP–C = 33.6 Hz, PCH2), 31.7
[Au(S2){P(p-MeOC6H4)3}] Workup method B, washed with
(CHCH3), 34.4 (CH2), 48.1 (NCH2), 122.2 (C-5 py), 122.4 (C-3
py), 128.9 (d, 3JP–C = 11.4 Hz, m-PPh2), 130.7 (d, 1JP–C = 54.3 Hz,
i-PPh2), 131.1 (p-PPh2), 133.5 (d, 2JP–C = 13.9 Hz, o-PPh2), 135.05
(C-4 py), 148.13 (C-6 py), 156.63 (CN), 158.46 (CN), 172.67 (CS)
ppm. Elemental analysis calcd. (%) for C55H64Au2N8P2S2 (1357.16
g mol-1): C 48.67, H 4.75 N 8.26, S 4.73; found: C 48.11, H 4.25,
N 8.04, S 4.25.
1
hexane: yellow solid. Yield: 0.052 g (79%). H NMR (400 MHz,
CDCl3): d = 2.62 (s, 3H, NCCH3), 3.37 (s, 6H, NMe2), 3.82 (s,
9H, OMe), 6.43 (dt, J = 7.9, 1.7 Hz, 1H, H-4 py), 6.62 (ddd,
J = 7.4, 4.9, 1.1 Hz, 1H, H-5 py), 6.83 (d, J = 8.1 Hz, 6H, H-
3
3¢ P(p-C6H4OMe)3), 7.18 (dd, JH–P = 11.7 Hz, J = 8.7 Hz, 6H,
H-2¢ P(p-C6H4OMe)3), 8.27 (d, J = 7.9 Hz, 1H, H-3 py), 8.34
1
(dd, J = 4.8, 0.8 Hz, 1H, H-6 py) ppm. 31P{ H} NMR (162 MHz,
[Au2(S1)2(l-dppb)] Workup method A: yellow crystals. Yield:
1
CDCl3): d = 33.8 ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.1
1
0.059 g (76%). H NMR (400 MHz, CDCl3): d = 0.96 (d, J =
(NCCH3), 40.0 (NMe2), 55.3 (OMe), 114.3 (d, 3JP–C = 12.5 Hz, C-
3¢ P(p-C6H4OMe)3), 121.9 (C-5 py), 122.2 (d, 1JP–C = 61.6 Hz, C-1¢
6.2 Hz, 6H, CHCH3), 1.12 (m, 4H, PCH2CH2), 1.29 (qd, J =
12.1, 2.3 Hz, 4H, CHax), 1.49 (m, 4H, PCH2), 1.68 (m, 6H, CHeq,
CHCH3), 2.53 (s, 6H, NCCH3), 3.00 (dt, J = 12.6, 1.8 Hz, 4H,
NCHax), 5.00 (d, J = 13.1 Hz, 4H, NCHeq), 6.49 (dt, J = 7.7,
1.7 Hz, 2H, H-4 py), 6.74 (ddd, 2H, H-5 py), 7.34–7.45 (m, 12H,
m-PPh2, p-PPh2), 7.49–7.58 (m, 8H, o-PPh2), 8.08 (d, J = 8.0 Hz,
P(p-C6H4OMe)3), 122.4 (C-3 py), 134.8 (C-4 py), 135.4 (d, 2JP–C
=
15.5 Hz, C-2¢ P(p-C6H4OMe)3), 147.8 (C-6 py), 156.3 (CN), 158.3
(CN), 161.7 (d, 4JP–C = 2.0 Hz, C-4¢ P(p-C6H4OMe)3), 172.1 (CS)
ppm. Elemental analysis calcd. (%) for C31H34AuN4O3PS (770.63
g mol-1): C 48.32, H 4.45, N 7.27, S 4.16; found: C 47.98, H 4.51,
N 7.24, S 3.84.
[Au(S2)(PTA)] Workup method B, washed with diethyl ether:
yellow solid. Yield: 0.061 g (83%). 1H NMR (400 MHz, CDCl3):
d = 2.59 (s, 3H, NCCH3), 3.32 (s, 6H, NMe2), 3.70 (s, 6H, PCH2N),
4.33 (ABquart, 2JH–H = 14.8 Hz, 6H, NCH2N), 7.32 (ddd, J = 7.2, 4.9,
1.2 Hz, 1H, H-5 py), 7.78 (t, J = 7.4, 1.2 Hz, 1H, H-4 py), 8.08 (d,
J = 7.4, 1.4 Hz, 1H, H-3 py), 8.70 (d, J = 3.8 Hz, 1H, H-6 py) ppm.
1
2H, H-3 py), 8.19 (m, 2H, H-6 py) ppm. 31P{ H} NMR (162 MHz,
1
CDCl3): d = 31.9 ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.1
2
(NCCH3), 21.9 (CHCH3), 26.7 (d, JP–C = 4.5 Hz, PCH2CH2),
27.7 (d, 1JP–C = 34.3 Hz, PCH2), 31.7 (CHCH3), 34.3 (CH2), 48.2
(NCH2), 122.0 (C-5 py), 122.3 (C-3 py), 128.8 (d, 3JP–C = 11.3 Hz,
m-PPh2), 131.1 (p-PPh2), 131.3 (d, 1JP–C = 53.7 Hz, i-PPh2), 133.2
(d, 2JP–C = 13.7 Hz, o-PPh2), 134.9 (C-4 py), 148.1 (C-6 py), 156.4
(CN), 158.4 (CN), 172.6 (CS) ppm. Elemental analysis calcd. (%)
for C56H66Au2N8P2S2 (1371.19 g mol-1): C 49.05, H 4.85, N 8.17,
S 4.68; found: C 48.69, H 4.91, N 8.14, S 4.57.
1
1
31P{ H} NMR (162 MHz, CDCl3): d = -51.0 ppm. 13C{ H} NMR
(101 MHz, CDCl3): d = 15.5 (NCCH3), 40.1 (NMe2), 53.0 (d,
1JP–C = 20.0 Hz, PCH2N), 73.2 (d, 3JP–C = 7.6 Hz, NCH2N), 122.2
(C-5 py), 123.3 (C-3 py), 135.4 (C-4 py), 148.9 (C-6 py), 156.7
(CN), 159.8 (CN), 173.9 (CS) ppm. Elemental analysis calcd. (%)
for C16H25AuN7PS (575.42 g mol-1): C 33.46, H 4.38, N 17.04, S
5.57; found: C 32.39, H 4.30, N 16.40, S 4.99.
[Au2(S1)2(l-dppf)] Workup method A: yellow solid. Yield: 0.051
g (69%). 1H NMR (400 MHz, CDCl3): d = 0.95 (d, J = 5.9 Hz, 6H,
CHCH3), 1.30 (m, J = 11.2 Hz, 4H, CHax), 1.70 (m, J = 11.3 Hz,
6H, CHeq, CHCH3), 2.56 (s, 6H, NCCH3), 3.01 (t, J = 12.3 Hz,
4H, NCHax), 3.87 (s, 4H, PC5H4), 4.61 (s, 4H, PC5H4), 5.02 (d,
J = 12.2 Hz, 4H, NCHeq), 6.43 (dt, J = 7.6, 0.8 Hz, 2H, H-4 py),
6.59 (dt, J = 4.9, 0.8 Hz, 2H, H-5 py), 7.18–7.32 (m, 16H, m-PPh2,
o-PPh2), 7.36 (m, 4H, p-PPh2), 8.16 (d, J = 7.6 Hz, 2H, H-3 py),
[Au2(S2)2(l-dppm)] Workup method A: yellow solid. Yield:
1
0.047 g (72%). H NMR (400 MHz, CDCl3): d = 2.57 (s, 6H,
NCCH3), 2.59 (m, 2H, PCH2), 3.38 (s, 12H, NMe2), 6.34 (dt, J =
8.0, 1.0 Hz, 2H, H-4 py), 6.65 (ddd, J = 7.6, 5.0, 1.1 Hz, 2H,
H-5 py), 7.21–7.28 (m, 8H, m-PPh2), 7.32–7.40 (m, 12H, o-PPh2,
p-PPh2), 8.10 (d, J = 7.8 Hz, 2H, H-3 py), 8.30 (ddd, J = 4.3,
1
8.28 (d, J = 4.4, 0.8 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162
1
MHz, CDCl3): d = 31.5 ppm. 13C{ H} NMR (101 MHz, CDCl3):
d = 15.5 (NCCH3), 21.9 (CHCH3), 31.7 (CHCH3), 34.3 (CH2),
1
1.3, 0.9 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162 MHz, CDCl3):
48.3 (NCH2), 73.1 (d, 1JP–C = 65.4 Hz, C-1¢ PC5H4), 74.0 (d, 2JP–C
=
13.1 Hz, C-2¢ PC5H4), 75.3 (d, 3JP–C = 8.2 Hz, C-3¢ PC5H4), 122.0
(C-5 py), 122.3 (C-3 py), 128.5 (d, 3JP–C = 11.4 Hz, m-PPh2), 130.9
(d, 4JP–C = 2.2 Hz, p-PPh2), 131.6 (d, 1JP–C = 56.8 Hz, i-PPh2), 133.4
(d, 2JP–C = 14.2 Hz, o-PPh2), 134.8 (C-4 py), 148.0 (C-6 py), 157.0
(CN), 158.1 (CN), 171.7 (CS) ppm. Elemental analysis calcd. (%)
for C62H66Au2FeN8P2S2 (1499.10 g mol-1): C 49.67, H 4.44, N 7.47,
S 4.28; found: C 48.96, H 4.44, N 7.35, S 4.04.
d = 26.8 ppm. Elemental analysis calcd. (%) for C45H48Au2N8P2S2
(1220.93 g mol-1): C 44.27, H 3.96, N 9.18, S 5.25; found: C 44.19,
H 4.06, N 9.17, S 5.05.
[Au2(S2)2(l-dppe)] Workup method A: yellow solid. Yield: 0.044
1
g (61%). H NMR (400 MHz, CDCl3): d = 2.10 (s, 4H, PCH2),
2.58 (s, 6H, NCCH3), 3.39 (s, 12H, NMe2), 6.39 (dt, J = 7.7,
1.3 Hz, 2H, H-4 py), 6.62 (dd, J = 1.3 Hz, 2H, H-5 py), 7.28–7.45
(m, 20H, PPh2), 7.96 (d, J = 7.9 Hz, 2H, H-3 py), 8.22 (d, J =
[Au(S2)PPh3] Workup method B, washed with hexane: yellow
solid. Yield: 0.108 g (78%). 1H NMR (400 MHz, CDCl3): d = 2.62
(s, 3H, NCCH3), 3.37 (s, 6H, NMe2), 6.33 (dt, J = 7.7, 1.7 Hz, 1H,
H-4 py), 6.58 (ddd, J = 7.2, 5.1, 0.6 Hz, 1H, H-5 py), 7.34 (m, 15H,
PPh3), 8.20 (d, J = 8.0 Hz, 1H, H-3 py), 8.31 (m, 1H, H-6 py) ppm.
1
3.9 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162 MHz, CDCl3): d =
1
35.9 ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.6 (NCCH3),
24.6 (ABX-t, PCH2), 40.1 (NMe2), 122.1 (C-5 py), 122.2 (C-3 py),
129.1 (ABX-t, m-PPh2), 129.8 (ABX-t, i-PPh2), 131.4 (p-PPh2),
133.1 (ABX-t, o-PPh2), 134.8 (C-4 py), 148.4 (C-6 py), 157.1 (CN),
158.4 (CN), 173.0 (CS) ppm. Elemental analysis calcd. (%) for
C46H50Au2N8P2S2 (1234.95 g mol-1): C 44.74, H 4.08, N 9.07, S
5.19; found: C 44.18, H 3.93, N 8.94, S 4.86.
1
1
31P{ H} NMR (162 MHz, CDCl3): d = 37.7 ppm. 13C{ H} NMR
(101 MHz, CDCl3): d = 15.3 (NCCH3), 40.0 (NMe2), 121.9 (C-5
py), 122.3 (C-3 py), 128.8 (d, 3JP–C = 11.4 Hz, m-PPh3), 130.2 (d,
1JP–C = 54.6 Hz, i-PPh3), 131.2 (p-PPh3), 134.0 (d, 2JP–C = 13.9 Hz,
o-PPh3), 134.8 (C-4 py), 147.9 (C-6 py), 156.6 (CN), 158.3 (CN),
172.3 (CS) ppm. Elemental analysis calcd. (%) for C28H28AuN4PS
(680.55 g mol-1): C 49.42, H 4.15, N 8.23, S 4.71; found: C 48.89,
[Au2(S2)2(l-dppee)] Workup method A: yellow solid. Yield:
1
0.045 g (63%). H NMR (400 MHz, CDCl3): d = 2.58 (s, 6H,
NCCH3), 3.40 (s, 12H, NMe2), 5.80 (m, 2H, PCH), 6.62 (dt,
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J = 7.6, 1.8 Hz, 2H, H-4 py), 6.82 (dt, J = 5.2, 1.6 Hz, 2H, H-
5 py), 7.16–7.44 (m, 20H, PPh2), 8.10 (d, J = 7.7 Hz, 2H, H-3 py),
[Au(S3)(PPh3)] Workup method A: yellow solid. Yield: 0.038 g
(55%). 1H NMR (CDCl3): d = 2.50 (s, 3H, NCCH3), 2.62 (s, 3H,
SMe), 7.04 (ddd, J = 7.7, 5.1, 1.5 Hz, 1H, H-5 py), 7.22 (dt, J = 7.7,
1.6 Hz, 1H, H-4 py), 7.38–7.55 (m, 15H, PPh3), 8.31 (d, J = 7.8 Hz,
1
8.39 (dd, J = 3.8, 0.9 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162
1
MHz, CDCl3): d = 23.4 ppm. 13C{ H} NMR (101 MHz, CDCl3):
1
d = 14.7 (NCCH3), 40.2 (NMe2), 121.7 (C-5 py), 122.7 (C-3 py),
129.1 (ABX-t, m-PPh2), 130.2 (ABX-t, i-PPh2), 131.2 (p-PPh2),
133.8 (ABX-t, o-PPh2), 134.9 (C-4 py), 138.1 (m, PCH), 147.9 (C-
6 py), 155.4 (CN), 158.8 (CN), 173.0 (CS) ppm. Elemental analysis
calcd. (%) for C46H48Au2N8P2S2 (1232.94 g mol-1): C 44.81, H 3.92,
N 9.09, S 5.20; found: C 44.30, H 3.77, N 9.04, S 4.86. Crystals
suitable for X-ray diffraction were grown by slow diffusion of
diethyl ether into a CDCl3/CH2Cl2 solution of the complex.
[Au2(S2)2(l-dppp)] Workup method A: yellow solid. Yield: 0.041
1H, H-3 py), 8.51 (m, 1H, H-6 py) ppm. 31P{ H} NMR (CDCl3):
1
d = 37.7 ppm. 13C{ H} NMR (CDCl3): d = 14.2 (NCCH3), 16.7
(SCH3), 121.9 (C-3 py), 123.4 (C-5 py), 129.1 (d, 3JP–C = 11.5 Hz,
m-PPh3), 129.6 (d, 1JP–C = 60.0 Hz, i-PPh3), 131.6 (d, 4JP–C = 2.2 Hz,
p-PPh3), 134.2 (d, 2JP–C = 13.9 Hz, o-PPh3), 135.6 (C-4 py), 148.3
(C-6 py), 156.7 (CN), 161.2 (CN), 166.3 (CS) ppm. Elemental
analysis calcd. (%) for C27H25AuN3PS2 (638.58 g mol-1): C 47.44,
H 3.69, N 6.15, S 9.38; found: C 47.03, H 3.66, N 6.08, S 9.14.
[Au(S3){P(p-MeOC6H4)3}] Workup method B, washed with
1
1
g (60%). H NMR (400 MHz, CDCl3): d = 1.15–1.31 (m, 2H,
hexane: yellow solid. Yield: 0.012 g (17%). H NMR (400 MHz,
PCH2CH2), 1.88 (m, 4H, PCH2), 2.55 (s, 6H, NCCH3), 3.38 (s,
12H, NMe2), 6.37 (dt, J = 7.6, 1.7 Hz, 2H, H-4 py), 6.76 (ddd, J =
7.3, 5.9, 1.0 Hz, 2H, H-5 py), 7.29–7.54 (m, 20H, PPh2), 7.97 (d,
J = 7.8 Hz, 2H, H-3 py), 8.32 (d, J = 4.2 Hz, 2H, H-6 py) ppm.
CDCl3): d = 2.50 (s, 3H, NCCH3), 2.62 (s, 3H, SMe), 3.84 (s,
9H, OMe), 6.92 (m, 6H, H-3¢ P(p-C6H4OMe)3), 6.94 (ddd, J =
7.4, 4.8, 1.2 Hz, 1H, H-5 py), 7.30 (dt, J = 7.6, 1.8 Hz, 1H, H-
4 py), 7.40 (m, 6H, H-2¢ P(p-C6H4OMe)3), 8.34 (d, J = 8.1 Hz,
1H, H-3 py), 8.53 (ddd, J = 4.8, 1.8, 0.9 Hz, 1H, H-6 py) ppm.
31P{ H} NMR (162 MHz, CDCl3): d = 31.7 ppm. 13C{ H} NMR
(101 MHz, CDCl3): d = 15.4 (NCCH3), 19.5 (m, PCH2CH2), 27.7
(dd, 1JP–C = 34.7 Hz, 3JP–C = 12.5 Hz, PCH2), 40.0 (NMe2), 122.2
(C-5 py), 122.4 (C-3 py), 128.9 (d, 3JP–C = 11.2 Hz, m-PPh2), 130.7
(d, 1JP–C = 53.9 Hz, i-PPh2), 131.1 (d, 4JP–C = 1.6 Hz, p-PPh2), 133.5
(d, 2JP–C = 13.8 Hz, o-PPh2), 135.0 (C-4 py), 148.1 (C-6 py), 156.4
(CN), 158.5 (CN), 173.1 (CS) ppm. Elemental analysis calcd. (%)
for C47H52Au2N8P2S2 (1248.98 g mol-1): C 45.20, H 4.20, N 8.97,
S 5.13; found: C 44.67, H 4.37, N 9.07, S 5.52.
1
1
1
1
31P{ H} NMR (162 MHz, CDCl3): d = 35.2 ppm. 13C{ H} NMR
(151 MHz, CDCl3): d = 14.4 (NCCH3), 16.8 (SCH3), 55.4 (OMe),
3
114.7 (d, JP–C = 13.3 Hz, C-3¢ P(p-C6H4OMe)3), 123.0 (C-3 py),
2
123.4 (C-5 py), 135.7 (d, JP–C = 15.6 Hz, C-2¢ P(p-C6H4OMe)3),
135.7 (C-4 py), 148.3 (C-6 py) ppm. Elemental analysis calcd. (%)
for C30H31AuN3O3PS2 (773.66 g mol-1): C 46.57, H 4.04, N 5.43, S
8.29; found: C 45.36, H 4.05, N 5.50, S 7.99.
[Au(S3)(PTA)] Workup method B, washed with diethyl ether:
1
[Au2(S2)2(l-dppb)] Workup method A: yellow solid. Yield: 0.060
g (85%). 1H NMR (400 MHz, CDCl3): d = 1.13 (s, 4H, PCH2CH2),
1.49 (s, 4H, PCH2), 2.55 (s, 6H, NCCH3), 3.37 (s, 12H, NMe2),
6.48 (t, J = 7.6 Hz, 2H, H-4 py), 6.74 (ddd, J = 6.3, 5.8, 0.7 Hz,
2H, H-5 py), 7.35–7.48 (m, 12H, m-PPh2, p-PPh2), 7.50–7.61 (m,
8H, o-PPh2), 8.07 (d, J = 8.0 Hz, 2H, H-3 py), 8.19 (d, J = 3.9 Hz,
yellow solid. Yield: 0.052 g (70%). H NMR (CDCl3): d = 2.50
(s, 3H, NCCH3), 2.59 (s, 3H, SMe), 3.94 (s, 6H, PCH2N), 4.39
(ABquart, 2JH–H = 13.6 Hz, 6H, NCH2N), 7.34 (dt, J = 5.2, 1.7 Hz,
1H, H-5 py), 7.78 (dt, J = 7.5, 1.4 Hz, 1H, H-4 py), 8.26 (d, J =
1
8.0 Hz, 1H, H-3 py), 8.68 (d, J = 4.5 Hz, 1H, H-6 py) ppm. 31P{ H}
1
NMR (CDCl3): d = -50.5 ppm. 13C{ H} NMR (CDCl3): d = 14.8
1
2H, H-6 py) ppm. 31P{ H} NMR (162 MHz, CDCl3): d = 33.9
(NCCH3), 16.6 (SCH3), 52.7 (d, 1JP–C = 19.7 Hz, PCH2N), 73.1 (d,
3JP–C = 7.7 Hz, NCH2N), 122.4 (C-3 py), 123.6 (C-5 py), 136.0 (C-4
py), 148.8 (C-6 py), 157.4 (Cipso–N), 161.9 (Cipso–N), 167.7 (C–S)
ppm. Elemental analysis calcd. (%) for C15H22AuN6PS2 (578.45 g
mol-1): C 31.15, H 3.83, N 14.53, S 11.09; found: C 31.15, H 3.89,
N 14.44, S 10.82.
1
ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.0 (NCCH3), 26.6
(dd, 2JP–C = 18.9 Hz, 3JP–C = 4.5 Hz, PCH2CH2), 27.7 (dd, 1JP–C
=
35.5 Hz, 4JP–C = 2.0 Hz, PCH2), 40.1 (NMe2), 121.9 (C-5 py), 122.3
(C-3 py), 128.9 (d, 3JP–C = 11.1 Hz, m-PPh2), 131.1 (p-PPh2), 131.2
1
2
(d, JP–C = 55.3 Hz, i-PPh2), 133.2 (d, JP–C = 13.5 Hz, o-PPh2),
134.9 (C-4 py), 148.1 (C-6 py), 156.1 (CN), 158.5 (CN), 173.1 (CS)
ppm. Elemental analysis calcd. (%) for C48H54Au2N8P2S2 (1263.01
g mol-1): C 45.65, H 4.31, N 8.87, S 5.08; found: C 44.77, H 4.28,
N 8.42, S 4.58.
[Au2(S3)2(l-dppe)] Workup method A: yellow solid. Yield: 0.053
g (61%). 1H NMR (CDCl3): d = 2.50 (s, 6H, NCCH3), 2.61 (s, 10H,
SMe, PCH2), 7.08 (dt, J = 7.7, 1.3 Hz, 2H, H-5 py), 7.27 (dt, J =
7.9, 1.7 Hz, 2H, H-4 py), 7.40–7.45 (m, 12H, p-PPh2, o-PPh2), 7.62
(d, J = 6.2 Hz, m-PPh2), 8.25 (d, J = 8.0 Hz, 2H, H-3 py), 8.50 (dd,
[Au2(S2)2(l-dppf)] Workup method A: yellow solid. Yield: 0.053
g (78%). 1H NMR (400 MHz, CDCl3): d = 2.58 (s, 6H, NCCH3),
3.38 (s, 12H, NMe2), 3.87 (s, 4H, H-2¢ PC5H4), 4.60 (s, 4H, H-3¢
PC5H4), 6.41 (dt, J = 7.7, 1.5 Hz, 2H, H-4 py), 6.58 (ddd, J = 7.2,
4.8, 0.9 Hz, 2H, H-5 py), 7.19–7.30 (m, 16H, m-PPh2, o-PPh2), 7.35
(m, 4H, p-PPh2), 8.12 (d, J = 7.8 Hz, 2H, H-3 py), 8.28 (d, J = 4.6,
1
J = 4.8, 1.6 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (CDCl3): d = 37.7
1
ppm. 13C{ H} NMR (CDCl3): d = 14.4 (NCCH3), 16.7 (SMe), 24.4
(PCH2), 121.8 (C-3 py), 123.6 (C-5 py), 128.6 (ABX-t, i-PPh2),
129.5 (ABX-t, m-PPh2), 132.1 (p-PPh2), 133.3 (ABX-t, o-PPh2),
135.7 (C-4 py), 148.5 (C-6 py), 156.6 (CN), 161.6 (CN), 165.5 (CS)
ppm. Elemental analysis calcd. (%) for C44H44Au2N6P2S4 (1241.01
g mol-1): C 42.58, H 3.57, N 6.77, S 10.34; found: C 42.48, H 3.60,
N 6.71, S 10.12.
1
0.9 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (162 MHz, CDCl3): d =
1
31.5 ppm.. 13C{ H} NMR (101 MHz, CDCl3): d = 15.5 (NCCH3),
40.1 (NMe2), 73.2 (d, 1JP–C = 65.3 Hz, C-1¢ PC5H4), 74.0 (d, 2JP–C
=
13.3 Hz, C-2¢ PC5H4), 75.3 (d, 3JP–C = 8.1 Hz, C-3¢ PC5H4), 122.0
(C-5 py), 122.3 (C-3 py), 128.5 (d, 3JP–C = 11.4 Hz, m-PPh2), 130.9
(d, 4JP–C = 2.1 Hz, p-PPh2), 131.6 (d, 1JP–C = 56.7 Hz, i-PPh2), 133.4
(d, 2JP–C = 14.2 Hz, o-PPh2), 134.8 (C-4 py), 148.0 (C-6 py), 156.8
(CN), 158.2 (CN), 172.4 (CS) ppm. Elemental analysis calcd. (%)
for C54H54Au2FeN8P2S2 (1390.92 g mol-1): C 46.63, H 3.91, N 8.06,
S 4.61; found: C 46.41, H 3.89, N 8.00, S 4.36.
[Au2(S3)2(l-dppp)] Workup method B, washed with diethyl
ether: yellow solid. Yield: 0.045 g (63%). H NMR (CDCl3): d =
1
1.74 (br. s, 2H, PCH2CH2), 2.46 (s, 10H, PCH2, NCCH3), 2.59 (s,
6H, SMe), 7.08 (dt, J = 7.3, 4.8, 1.0 Hz, 2H, H-5 py), 7.15 (dt,
J = 7.0, 1.0 Hz, 2H, H-4 py), 7.32–7.49 (m, 12H, p-PPh2, m-PPh2),
7.62 (m, 8H, o-PPh2), 8.20 (d, J = 8.1 Hz, 2H, H-3 py), 8.51 (d,
1
J = 4.8 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (CDCl3): d = 32.5
9816 | Dalton Trans., 2011, 40, 9810–9820
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1
ppm. 13C{ H} NMR (CDCl3): d = 14.4 (NCCH3), 16.7 (SMe), 20.0
[Au(Se1)(PPh3)] Workup method B, washed with pentane: light
yellow crystals. Yield: 0.073 g (93%). 1H NMR (400 MHz, CDCl3):
d = 0.95 (d, J = 6.1 Hz, 3H, CHCH3), 1.29 (qd, J = 11.3, 1.9 Hz, 2H,
CHax), 1.67 (m, 3H, CHeq, CHCH3), 2.58 (s, 3H, NCCH3), 3.03
(t, J = 12.5 Hz, 2H, NCHax), 4.99 (d, J = 13.2 Hz, 2H, NCHeq),
6.53 (dt, J = 7.2, 1.5 Hz, 1H, H-4 py), 6.63 (m, 1H, H-5 py), 7.25
(m, 6H, m-PPh3), 7.33 (dt, J = 7.8, 2.7 Hz, 6H, o-PPh3), 7.42 (dt,
J = 7.4, 2.0 Hz, 3H, p-PPh3), 8.32 (d, J = 4.4 Hz, 1H, H-6 py),
2
1
3
(t, JP–C = 4.0 Hz, PCH2CH2), 28.3 (dd, JP–C = 34.6 Hz, JP–C
=
=
12.3 Hz, PCH2), 122.0 (C-3 py), 123.6 (C-5 py), 129.3 (d, 3JP–C
4
11.3 Hz, m-PPh2), 129.5 (d, i-PPh2), 131.7 (d, JP–C = 1.8 Hz, p-
PPh2), 133.4 (d, JP–C = 13.5 Hz, o-PPh2), 135.7 (C-4 py), 148.4
(C-6 py), 156.8 (CN), 161.5 (CN), 167.1 (CS) ppm. Elemental
analysis calcd. (%) for C45H46Au2N6P2S4 (1255.03 g mol-1): C
43.07, H 3.69, N 6.70, S 10.22; found: C 42.95, H 3.79, N 7.06,
S 10.24.
2
1
8.37 (d, J = 7.8 Hz, 1H, H-3 py) ppm. 31P{ H} NMR (162 MHz,
1
CDCl3): d = 38.3 ppm. 13C{ H} NMR (101 MHz, CDCl3): d =
[Au2(S3)2(l-dppb)] Workup method A: yellow solid. Yield: 0.050
g (71%). 1H NMR (CDCl3): d = 1.62 (br. s, 4H, PCH2CH2), 2.14
(br. s, 4H, PCH2), 2.49 (s, 6H, NCCH3), 2.61 (s, 6H, SMe), 7.08
(ddd, J = 7.4, 4.9, 1.1 Hz, 2H, H-5 py), 7.24 (dt, J = 7.8, 1.6 Hz,
2H, H-4 py), 7.40–7.52 (m, 12H, p-PPh2, m-PPh2), 7.57–7.67 (m,
8H, o-PPh2), 8.26 (d, J = 8.0 Hz, 2H, H-3 py), 8.48 (d, J = 4.1 Hz,
15.3 (NCCH3), 21.8 (CHCH3), 31.8 (CHCH3), 34.3 (CH2), 49.6
(NCH2), 122.1 (C-5 py), 122.2 (C-3 py), 128.8 (d, 3JP–C = 11.4 Hz,
m-PPh3), 130.5 (d, 1JP–C = 54.7 Hz, i-PPh3), 131.0 (d, 4JP–C = 2.4 Hz,
p-PPh3), 134.0 (d, 2JP–C = 14.0 Hz, o-PPh3), 134.8 (C-4 py), 147.9
(C-6 py), 157.4 (CN), 158.0 (CN), 166.8 (CSe) ppm. Elemental
analysis calcd. (%) for C32H34AuN4PSe (781.54 g mol-1): C 49.18,
H 4.38, N 7.17; found: C 46.65, H 4.44, N 7.03.
2H, H-6 py) ppm. 31P{ H} NMR (CDCl3): d = 35.1 ppm. 13C{ H}
1
1
NMR (CDCl3): d = 14.3 (NCCH3), 16.7 (SMe), 26.8 (dd, 2JP–C
=
17.8, 3JP–C = 4.7 Hz, PCH2CH2), 27.9 (d, 1JP–C = 34.9 Hz, PCH2),
121.9 (C-3 py), 123.5 (C-5 py), 129.2 (d, 3JP–C = 11.4 Hz, m-PPh2),
[Au(Se1)(PTA)] Workup method B, washed with hexane: yellow
solid. Yield: 0.172 g (99%). 1H NMR (400 MHz, CDCl3): d = 0.95
(d, J = 6.0 Hz, 3H, CHCH3), 1.26 (m, 2H, CHax), 1.66 (m, 3H,
CHeq, CHCH3), 2.57 (s, 3H, NCCH3), 3.01 (t, J = 12.5 Hz, 2H,
NCHax), 3.63 (s, 6H, PCH2N), 4.28 (ABquart, 2JH–H = 13.7 Hz, 6H,
NCH2N), 4.91 (d, J = 11.3 Hz, 2H, NCHeq), 7.32 (dt, J = 5.7,
1.3 Hz, 1H, H-5 py), 7.77 (dt, J = 7.7, 1.7 Hz, 1H, H-4 py), 8.19
(d, J = 7.9 Hz, 1H, H-6 py), 8.69 (d, J = 3.3 Hz, 1H, H-3 py)
129.9 (d, 1JP–C = 54.6 Hz, i-PPh2), 131.7 (p-PPh2), 133.2 (d, 2JP–C
=
13.5 Hz, o-PPh2), 135.7 (C-4 py), 148.4 (C-6 py), 156.7 (CN),
161.3 (CN), 166.7 (CS) ppm. Elemental analysis calcd. (%) for
C46H48Au2N6P2S4 (1269.05 g mol-1): C 43.54, H 3.81, N 6.02, S
10.11; found: C 41.22, H 3.60, N 6.23, S 9.45. Crystals suitable
for X-ray diffraction were grown by slow diffusion of diethyl ether
into a CDCl3/CH2Cl2 solution of the complex.
1
1
ppm. 31P{ H} NMR (162 MHz, CDCl3): d = -48.7 ppm. 13C{ H}
NMR (101 MHz, CDCl3): d = 15.6 (NCCH3), 21.8 (CHCH3),
31.6 (CHCH3), 34.2 (CH2), 49.7 (NCH2), 52.8 (d, 1JP–C = 18.8 Hz,
PCH2N), 73.1 (d, 3JP–C = 7.5 Hz, NCH2N), 122.4 (C-5 py), 123.2
(C-3 py), 135.4 (C-4 py), 148.8 (C-6 py), 157.5 (CN), 159.3 (CN),
168.7 (CSe) ppm. 77Se NMR (76 MHz, CDCl3, Me2Se): d = 39
ppm. Elemental analysis calcd. (%) for C20H31AuN7PSe (676.41 g
mol-1): C 35.51, H 4.62, N 14.50; found: C 35.25, H 4.94, N 14.14.
[Au2(Se1)2(l-dppm)] Workup method B, washed with hexane:
yellow crystals. Yield: 0.130 g (78%). 1H NMR (400 MHz, CDCl3):
d = 0.94 (d, J = 6.1 Hz, 6H, CHCH3), 1.29 (qd, J = 11.7, 2.3 Hz, 4H,
CHax), 1.68 (m, 6H, CHeq, CHCH3), 2.47 (s, 6H, NCCH3), 2.76 (t,
2JH–P = 10.6 Hz, 2H, PCH2), 3.04 (dt, J = 12.6, 1.5 Hz, 4H, NCHax),
5.04 (d, J = 13.0 Hz, 4H, NCHeq), 6.67 (dt, J = 7.5, 1.5 Hz, 2H,
H-4 py), 6.71 (m, 2H, H-5 py), 7.20 (t, J = 7.5 Hz, 8H, m-PPh2),
7.32 (m, 12H, o-PPh2, p-PPh2), 8.29 (dd, J = 4.7, 1.1 Hz, 2H, H-6
[Au2(S3)2(l-dppf)] Workup method A: yellow solid. Yield: 0.043
g (62%). 1H NMR (CDCl3): d = 2.49 (s, 6H, NCCH3), 2.65 (s, 6H,
SMe), 4.23 (s, 4H, PC5H4), 4.76 (s, 4H, PC5H4), 7.12 (ddd, J = 7.3,
4.9, 1.0 Hz, 2H, H-5 py), 7.40 (m, 10H, H-4 py, m-PPh2), 7.41–
7.56 (m, 12H, o-PPh2, p-PPh2), 8.33 (d, J = 8.0 Hz, 2H, H-3 py),
8.55 (d, J = 4.1 Hz, 2H, H-6 py) ppm. 31P{ H} NMR (CDCl3):
1
d = 33.5 ppm. 13C{ H} NMR (CDCl3): d = 14.1 (NCCH3), 16.9
1
1
2
(SCH3), 71.9 (d, JP–C = 65.7 Hz, C-1¢ PC5H4), 74.6 (d, JP–C
=
12.8 Hz, C-2¢ PC5H4), 75.4 (d, 3JP–C = 5.0 Hz, C-3¢ PC5H4), 121.8
(C-3 py), 123.5 (C-5 py), 129.0 (d, 3JP–C = 11.6 Hz, m-PPh2), 130.9
(d, 1JP–C = 58.6 Hz, i-PPh2), 131.5 (d, 4JP–C = 1.9 Hz, p-PPh2), 133.5
(d, 2JP–C = 14.0 Hz, o-PPh2), 135.8 (C-4 py), 148.4 (C-6 py), 156.6
(CN), 161.1 (CN), 165.3 (CS) ppm. Elemental analysis calcd. (%)
for C52H48Au2FeN6P2S4 (1396.97 g mol-1): C 44.71, H 3.46, N 6.02,
S 9.18; found: C 44.25, H 3.46, N 5.85, S 8.92.
1
py), 8.38 (d, J = 7.7 Hz, 2H, H-3 py) ppm. 31P{ H} NMR (162
1
MHz, CDCl3): d = 27.8 ppm. 13C{ H} NMR (101 MHz, CDCl3):
Preparation of the gold selenosemicarbazone complexes. All
reactions were carried out in vessels shielded from light. To a
solution of the selenosemicarbazone (HSe1 or HSe2) in ethanol
(10 mL) was added 25 mL of a 50% aqueous KOH solution. After
stirring for ca. 10 min. the solid phosphine gold chloride (0.9
equivalent) was added and the mixture was refluxed for one hour.
Two workup methods were used:
d = 14.5 (NCCH3), 21.9 (CHCH3), 28.6 (t, 1JP–C = 25.0 Hz, PCH2),
31.7 (CHCH3), 34.4 (CH2), 49.6 (NCH2), 121.7 (C-3 py), 122.0
(C-5 py), 128.8 (ABX-t, m-PPh2), 129.6 (ABX-t, i-PPh2), 131.3 (p-
PPh2), 133.2 (ABX-t, o-PPh2), 134.9 (C-4 py), 147.7 (C-6 py), 155.8
(CN), 158.0 (CN), 167.2 (CSe) ppm. Elemental analysis calcd. (%)
for C53H60Au2N8P2Se2 (1422.90 g mol-1): C 44.74, H 4.25, N 7.88;
found: C 43.53, H 4.29, N 7.84.
A) When a suspension formed the solid was isolated by
filtration, washed with methanol, water and diethyl ether and
subsequently dried in air.
B) When a solution formed, the mixture was evaporated to
dryness and the residue was dissolved in dichloromethane and
passed through celite. The solution was concentrated and the
products precipitated upon addition of a suitable solvent such
as diethyl ether, hexane or pentane. The solids were isolated by
filtration and subsequently dried in air.
[Au2(Se1)2(l-dppb)] Workup method A: yellow crystals. Yield:
0.138 g (84%). 1H NMR (400 MHz, CDCl3): d = 0.96 (d, J = 5.9 Hz,
6H, CHCH3), 1.15 (br. s, 4H, PCH2CH2), 1.29 (m, 4H, CHax), 1.49
(s, 4H, PCH2), 1.67 (m, 6H, CHeq, CHCH3), 2.51 (s, 6H, NCCH3),
3.03 (t, J = 12.8 Hz, 4H, NCHax), 4.98 (d, J = 11.7 Hz, 4H, NCHeq),
6.62 (dt, J = 7.6, 1.8 Hz, 2H, H-4 py), 6.77 (m, 2H, H-5 py), 7.33–
7.46 (m, 12H, m-PPh2, p-PPh2), 7.53 (m, 8H, o-PPh2), 8.22 (m,
1
2H, H-6 py), 8.23 (m, 2H, H-3 py) ppm. 31P{ H} NMR (162
1
MHz, CDCl3): d = 34.3 ppm. 13C{ H} NMR (101 MHz, CDCl3):
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1
d = 15.2 (NCCH3), 21.8 (CHCH3), 26.4 (dd, JP–C = 33.2 Hz,
158.0 (CN), 161.7 (d, 4JP–C = 2.0 Hz, C-4¢ P(p-C6H4OMe)3), 166.9
(CS) ppm. Elemental analysis calcd. (%) for C31H34AuN4O3PSe
(817.53 g mol-1): C 45.54, H 4.19, N 6.85; found: C 45.08, H 3.86,
N 6.97.
PCH2), 27.6 (d, 2JP–C = 18.9 Hz, 3JP–C = 5.0 Hz, PCH2CH2), 31.7
(CHCH3), 34.3 (CH2), 49.6 (NCH2), 122.1 (C-5 py), 122.3 (C-
3 py), 128.8 (d, JP–C = 11.2 Hz, m-PPh2), 131.1 (p-PPh2), 131.3
(d, JP–C = 52.5 Hz, i-PPh2), 133.1 (d, JP–C = 13.7 Hz, o-PPh2),
134.9 (C-4 py), 148.0 (C-6 py), 157.1 (CN), 158.1 (CN), 167.8
(CSe) ppm. 77Se NMR (76 MHz, CDCl3, Me2Se): d = 44 ppm.
Elemental analysis calcd. (%) for C56H66Au2N8P2Se2 (1464.98 g
mol-1): C 45.91, H 4.54, N 7.65; found: C 45.53, H 4.78, N 7.57.
[Au2(Se1)2(l-dppf)] Workup method B, washed with diethyl
3
1
2
[Au2(Se2)2(l-dppm)] Workup method B, washed with hexane:
yellow solid. Yield: 0.042 g (53%). 1H NMR (400 MHz, CD2Cl2):
2
d = 2.42 (s, 6H, NCCH3), 2.52 (t, JH–P = 11.0 Hz, 2H, PCH2),
3.38 (s, 12H, NMe2), 6.74 (m, 2H, H-4 py, H-5 py), 7.16–7.24 (m,
8H, m-PPh2), 7.27–7.39 (m, 12H, o-PPh2, p-PPh2), 8.23 (m, 2H,
1
H-3 py), 8.36 (m, 2H, H-6 py) ppm. 31P{ H} NMR (162 MHz,
1
1
ether: yellow solid. Yield: 0.126 g (81%). H NMR (400 MHz,
CD2Cl2): d = 28.3 ppm. 13C{ H} NMR (101 MHz, CDCl3): d =
CDCl3): d = 0.95 (d, J = 5.9 Hz, 6H, CHCH3), 1.28 (m, 4H, CHax),
1.69 (m, 6H, CHeq, CHCH3), 2.56 (s, 6H, NCCH3), 3.05 (t, J =
12.9 Hz, 4H, NCHax), 3.90 (s, 4H, H-2¢ PC5H4), 4.64 (s, 4H, H-
3¢ PC5H4), 5.02 (d, J = 13.4 Hz, 4H, NCHeq), 6.63 (dt, J = 7.3,
1.5 Hz, 2H, H-4 py), 6.67 (m, 2H, H-5 py), 7.27 (m, 16H, m-PPh2,
o-PPh2), 7.39 (m, 4H, p-PPh2), 8.32 (d, J = 4.0, 1.2 Hz, 2H, H-6
14.8 (NCCH3), 41.3 (NMe2), 121.7 (C-5 py), 122.12 (C-3 py),
128.9 (ABX-t, m-PPh2), 131.5 (p-PPh2), 133.4 (ABX-t, o-PPh2),
135.0 (C-4), 147.9 (C-6 py), 168.1 (CSe) ppm. Elemental analysis
calcd. (%) for C45H48Au2N8P2Se2 (1314.72 g mol-1): C 41.11, H
3.68, N 8.52; found: C 39.85, H 3.67, N 8.06.
[Au2(Se2)2(l-dppe)] Workup method B, washed with hexane:
py), 8.35 (d, J = 7.5 Hz, 2H, H-3 py), 8.28 ppm. 31P{ H} NMR (162
yellow solid. Yield: 0.040 g (52%). H NMR (CDCl3): d = 2.12
1
1
MHz, CDCl3): d = 31.1 ppm. 13C{ H} NMR (101 MHz, CDCl3):
(s, 4H, PCH2), 2.57 (s, 6H, NCCH3), 3.41 (s, 12H, NMe2), 6.50
(dt, J = 7.5, 1.1 Hz, 2H, H-4 py), 6.67 (dt, J = 5.6, 1.1 Hz, 2H,
H-5 py), 7.28–7.36 (m, 16H, m-PPh2, o-PPh2), 7.36–7.44 (m, 4H,
p-PPh2), 8.10 (dd, J = 7.6 Hz, 2H, H-3 py), 8.23 (dd, J = 4.4 Hz,
1
d = 15.3 (NCCH3), 21.9 (CHCH3), 31.8 (CHCH3), 34.3 (CH2),
2
49.8 (NCH2), 73.1 (m, C-1¢ PC4H5), 74.0 (dd, JP–C = 13.1 Hz,
4JP–C = 13.1 Hz, C-2¢ PC4H5), 75.3 (m, C-3¢ PC4H5), 122.1 (C-5
3
1
1
py), 122.2 (C-3 py), 128.6 (d, JP–C = 9.5 Hz, m-PPh2), 130.9 (p-
2H, H-6 py) ppm. 31P{ H} NMR (CDCl3): d = 36.7 ppm. 13C{ H}
NMR (101 MHz, CDCl3, 300 K): d = 15.7 (NCCH3), 24.3 (m,
PCH2), 41.2 (NMe2), 122.1 (C-5 py), 122.2 (C-3 py), 129.1 (ABX-
t, m-PPh2), 129.8 (ABX-t, i-PPh2), 131.4 (p-PPh2), 133.1 (ABX-t,
o-PPh2), 134.9 (C-4 py), 148.3 (C-6 py), 157.9 (CN), 158.1 (C-2 py),
168.1 (CSe) ppm. 77Se NMR (76 MHz, CDCl3, Me2Se, 300 K) d =
42 (m) ppm. Elemental analysis calcd. (%) for C46H50Au2N8P2Se2
(1328.74 g mol-1): C 41.58, H 3.79, N 8.43; found: C 41.00, H 3.84,
N 8.50.
PPh2), 131.6 (d, 1JP–C = 56.1 Hz, i-PPh2), 133.4 (d, 2JP–C = 13.4 Hz,
o-PPh2), 134.9 (C-4 py), 147.9 (C-6 py), 157.5 (CN), 157.8 (CN),
166.4 (CSe) ppm. 77Se NMR (76 MHz, CDCl3, Me2Se): d = 35
ppm. Elemental analysis calcd. (%) for C62H66Au2FeN8P2Se2 · 1.5
CH2Cl2 (1720.28 g mol-1): C 44.33, H 4.04, N 6.51; found: C 44.52,
H 3.87, N 6.65. Crystals suitable for X-ray diffraction were grown
by slow diffusion of diethyl ether into a CDCl3/CH2Cl2 solution
of the complex.
[Au(Se2)(PPh3)] Workup method B, washed with hexane: light
yellow solid. Yield: 0.110 g (75%). 1H NMR (400 MHz, CDCl3):
d = 2.60 (s, 3H, NCCH3), 3.39 (s, 6H, NMe2), 6.48 (dt, J = 7.7,
1.6 Hz, 1H, H-4 py), 6.61 (ddd, J = 7.0, 5.0, 0.7 Hz, 1H, H-5
py), 7.26 (m, 6H, m-PPh3), 7.34 (m, 6H, o-PPh3), 7.42 (m, 3H,
p-PPh3), 8.30 (d, J = 4.7 Hz, 1H, H-6 py), 8.35 (d, J = 8.0 Hz,
[Au2(Se2)2(l-dppee)] Workup method B, washed with diethyl
ether: yellow solid. Yield: 0.133 mg (86%). H NMR (400 MHz,
1
CDCl3): d = 2.52 (s, 6H, NCCH3), 3.42 (s, 12H, NMe2), 6.32
(m, 2H, PCH), 6.80 (m, 4H, H-4 py, H-5 py), 7.23 (m, 8H, o-
PPh2), 7.35 (m, 12H, p-PPh2, m-PPh2), 8.33 (d, J = 7.7 Hz, 2H,
1
H-3 py), 8.36 (d, J = 3.6 Hz, 2H, H-6 py) ppm. 31P{ H} NMR
1
1
1H, H-3 py) ppm. 31P{ H} NMR (162 MHz, CDCl3): d = 38.2
(162 MHz, CDCl3): d = 19.8 ppm. 13C{ H} NMR (101 MHz,
1
ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.3 (NCCH3), 41.1
CDCl3, 300 K): d = 14.5 (NCCH3), 41.3 (NMe2), 121.7 (C-5 py),
122.3 (C-3 py), 129.0 (ABX-t, o-PPh2), 130.5 (ABX-t, i-PPh2),
131.2 (p-PPh2), 133.6 (ABX-t, m-PPh2), 135.0 (C-4 py), 139.5 (d,
1JP–C = 48.3 Hz, PCH) 147.8 (C-6 py), 155.7 (CN), 158.3 (C-
2 py), 167.4 (CSe) ppm. 77Se NMR (76 MHz, CDCl3, Me2Se)
d = 75 ppm. Elemental analysis calcd. (%) for C46H48Au2N8P2Se2
(1326.73 g mol-1): C 41.64, H 3.65, N 8.45; found C 41.33, H 3.71,
N 8.40.
(NMe2), 122.0 (C-5 py), 122.2 (C-3 py), 128.8 (d, 3JP–C = 11.3 Hz,
m-PPh3), 130.5 (d, 1JP–C = 54.5 Hz, i-PPh3), 131.0 (d, 4JP–C = 2.1 Hz,
p-PPh3), 134.0 (d, 2JP–C = 13.9 Hz, o-PPh3), 134.8 (C-4 py), 147.9
(C-6 py), 157.3 (CN), 158.1 (CN), 167.3 (CSe) ppm. 77Se NMR
(76 MHz, CDCl3, Me2Se) d = 34 ppm. Elemental analysis calcd.
(%) for C28H28AuN4PSe (727.45 g mol-1): C 45.87, H 3.88, N 7.70;
found: C 45.87, H 3.76, N 7.51.
[Au(Se2){P(p-MeOC6H4)3}] Workup method B, washed with
[Au2(Se2)2(l-dppb)] Workup method B, washed with diethyl
ether: yellow solid. Yield: 0.030 g (40%). H NMR (400 MHz,
1
1
hexane: yellow solid. Yield: 0.028 g (40%). H NMR (400 MHz,
CDCl3): d = 2.60 (s, 3H, NCCH3), 3.38 (s, 6H, NMe2), 3.81 (s,
9H, OMe), 6.56 (dt, J = 7.5, 0.8 Hz, 1H, H-4 py), 6.65 (dt, J =
7.1, 3.5, 1.1 Hz, 1H, H-5 py), 6.82 (d, J = 8.5 Hz, 6H, H-3¢ P(p-
CDCl3): d = 1.14 (s, 4H, PCH2CH2), 1.49 (s, 4H, PCH2), 2.53 (s,
6H, NCCH3), 3.39 (s, 12H, NMe2), 6.59 (t, J = 7.6 Hz, 2H, H-4
py), 6.76 (m, 2H, H-5 py), 7.35–7.47 (m, 12H, m-PPh2, p-PPh2),
7.51–7.59 (m, 8H, o-PPh2), 8.21 (m, 4H, H-3 py, H-6 py) ppm.
3
C6H4OMe)3), 7.17 (dd, JH–P = 11.9 Hz, J = 8.5 Hz, 6H, H-2¢
1
1
P(p-C6H4OMe)3), 8.34 (dd, J = 4.8, 0.8 Hz, 1H, H-6 py), 8.41
31P{ H} NMR (162 MHz, CDCl3): d = 34.4 ppm. 13C{ H} NMR
(101 MHz, CDCl3): d = 15.2 (NCCH3), 26.3 (m, PCH2CH2), 27.6
(d, 1JP–C = 34.4 Hz, PCH2), 41.17 (NMe2), 122.07 (C-5 py), 122.30
1
(dd, J = 7.7, 1.1 Hz, 1H, H-3 py) ppm. 31P{ H} NMR (162 MHz,
1
CDCl3): d = 34.7 ppm. 13C{ H} NMR (101 MHz, CDCl3): d = 15.1
(NCCH3), 41.1 (NMe2), 55.4 (OMe), 114.4 (d, 3JP–C = 12.4 Hz, C-
(C-3 py), 128.84 (d, JP–C = 11.4 Hz, m-PPh2), 131.09 (p-PPh2),
3
1
1
2
3¢ P(p-C6H4OMe)3), 121.9 (C-5 py), 122.2 (d, JP–C = 51.3 Hz,
131.36 (d, JP–C = 54.30 Hz, i-PPh2), 133.18 (d, JP–C = 13.8 Hz,
o-PPh2), 134.96 (C-4 py), 148.05 (C-6 py), 156.91 (CN), 158.22
(CN), 168.35 (CSe) ppm. 77Se NMR (76 MHz, CDCl3, KSeCN)
C-1¢ P(p-C6H4OMe)3), 122.3 (C-3 py), 134.9 (C-4 py), 135.4 (d,
2JP–C = 15.5 Hz, C-2¢ P(p-C6H4OMe)3), 147.8 (C-6 py), 157.0 (CN),
9818 | Dalton Trans., 2011, 40, 9810–9820
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d = 44 ppm. Elemental analysis calcd. (%) for C48H54Au2N8P2Se2
(1342.77 g mol-1): C 42.04, H 3.90, N 8.34; found: C 41.54, H 3.64,
N 7.80.
Synchronization
After reaching a parasitemia of approximately 0.5% or higher,
5 mL of cultures were centrifuged at 700 g for 5 min at room
temperature (RT). Packed red cells were resuspended in 3 mL of
5% D-sorbitol in water at RT and immediately centrifuged again
at 700 g for 5 min at RT followed by three washes with 3 mL of
RPMI 1640 medium.
[Au2(Se2)2(l-dppf)] Workup method B, washed with diethyl
1
ether: yellow solid. Yield: 0.058 g (79%). H NMR (400 MHz,
CDCl3): d = 2.56 (s, 6H, NCCH3), 3.39 (s, 12H, NMe2), 3.88 (s,
4H, H-2¢ PC5H4), 4.60 (s, 4H, H-3¢ PC5H4), 6.54–6.67 (m, 4H, H-4
py, H-5 py), 7.17–7.30 (m, 12H, o-PPh2, m-PPh2), 7.37.42- (m, 4H,
1
p-PPh2), 8.29 (m, 4H, H-3 py, H-6 py) ppm. 31P{ H} NMR (162
1
MHz, CDCl3): d = 32.4 ppm. 13C{ H} NMR (101 MHz, CDCl3):
1
d = 15.4 (NCCH3), 41.2 (NMe2), 73.0 (d, JP–C = 62.7 Hz, C-1¢
In vitro determination of IC50 values for growth inhibition
2
3
PC5H4), 74.0 (d, JP–C = 13.0 Hz, C-2¢ PC5H4), 75.3 (d, JP–C
=
Samples were diluted with RPMI 1640 medium containing 0.5%
Albumax II (GIBCO, Invitrogen, Vienna, Austria). A hematocrit
of 1.5% and a parasitemia of 0.05% were reached by adding
uninfected red blood cells. 150 mL of this cell medium mixture
was then added to each well of drug coated 96-well plates and
incubated at 37 ◦C for 72 h in a gas mixture containing 5% CO2,
5% O2, and 90% N2.
6.8 Hz, C-3¢ PC5H4), 122.1 (C-5 py), 122.2 (C-3 py), 128.5 (d,
3JP–C = 9.9 Hz, m-PPh2), 130.9 (p-PPh2), 131.6 (d, 1JP–C = 56.5 Hz,
2
i-PPh2), 133.3 (d, JP–C = 14.3 Hz, o-PPh2), 134.9 (C-4 py), 147.9
(C-6 py), 157.4 (CN), 157.9 (CN), 167.0 (CSe) ppm. 77Se NMR
(76 MHz, CDCl3, Me2Se, 300 K) d = 35 ppm. Elemental analysis
calcd. (%) for C54H54Au2FeN8P2Se2 (1484.71 g mol-1): C 43.68, H
3.67, N 7.55; found: C 42.62, H 3.31, N 7.31.
Evaluation of anti-malaria activity
Drug -coating of 96 well test plates
Plasmodium falciparum culture. The chloroquine-sensitive
3D7 strain was obtained from ATCC (Manassas, VA, USA).
Parasites were cultured in RPMI 1640 medium containing 10%
human serum at a hematocrit of 5% (blood group O negative).
Cultures were kept at 37 ◦C under an atmosphere of 5% CO2,
5% O2 and 90% N2. The medium was changed every 24 to 48 h
and fresh erythrocytes were added whenever the parasite density
reached 1%.
Stock solutions (10 mg mL-1) were prepared in pure DMSO to give
a final solvent concentration of 0.25%. These were diluted with
RPMI 1640 in order to obtain the desired test concentrations.
Seven serial 1 : 3 dilutions of the compounds (25 mL/well) were
dispensed into standard 96-well microculture plates (IWAKI, code
3860-096). One well contained solvent only. These plates were
either used immediately or frozen at -20 ◦C until further use.
Table 3 Crystal data, data collection and refinement parameters for HS1, HSe1 and the gold complexes [Au(S2)(PPh3)], Au2(S2)2(l-dppee)], [Au2(S3)2(l-
dppb)] and [Au2(Se1)2(l-dppf)]
HS1
HSe1
[Au(S2)(PPh3)]
[Au2(S2)2(m-dppee)] [Au2(S3)2(m-dppb)] [Au2(Se1)2(m-dppf)]
empirical formula
mol. wt. (g mol-1)
color, shape
C14 H20 N4 S
276.40
Yellow needle
Monoclinic
P21
8.4059(4)
4.8128(4)
17.6696(10)
90
92.275(4)
90
C14H20SeN4
323.30
Orange block
Orthorhombic
Pbca
12.7398(4)
9.0666(4)
26.1314(12)
90
90
90
3018.3(2)
200
8
C28H28N4AuSP
680.54
Yellow needle
Monoclinic
C2/c
23.6881(5)
12.9308(3)
18.0223(4)
90
99.015(2)
90
C23H24N4AuPS
616.46
Yellow block
Monoclinic
C2/c
11.6538(2)
18.3046(3)
21.4734(4)
90
92.6764(15)
90
C23H24N3AuPS2
634.51
C62H66Au2FeN8P2Se2
1592.87
Yellow block
Triclinic
Orange block
Triclinic
Crystal system
¯
¯
Space group
P1
P1
˚
a (A)
8.1598(3)
11.3329(6)
13.6971 (6)
104.614(4)
100.524(3)
101.158(4)
1166.19(9)
150
11.4658(2)
11.4760(2)
12.2708(2)
101.5540(10)
100.5610(10)
106.8280(10)
1463.18(4)
100
˚
b (A)
˚
c (A)
a (◦)
b (◦)
g (◦)
3
˚
V (A )
714.28(8)
100
2
5452.1(2)
150
8
4575.69(14)
150
4
T (K)
Z
1
1
Dc (g cm-3)
Crystal size (mm3)
m (mm-1)
1.285
1.423
1.658
1.790
1.807
0.19 ¥ 0.13 ¥ 0.10
6.570
2.83–29.42
9583
5374[R(int) =
0.0242]
0.0234
0.0492
0.994
0.898/-0.973
1.808
0.17 ¥ 0.14 ¥ 0.03
6.591
2.91–33.20
34667
11158[R(int) =
0.0310]
0.0259
0.0631
1.043
1.072/-1.940
0.32 ¥ 0.06 ¥ 0.06 0.18 ¥ 0.14 ¥ 0.12 0.11 ¥ 0.04 ¥ 0.04 0.60 ¥ 0.43 ¥ 0.18
0.219
2.46–33.15
14810
5436 [R(int) =
0.0433]
0.0407
0.1025
2.481
2.87–29.39
9738
3507[R(int) =
0.0227]
0.0347
0.0866
0.888
0.655/-0.572
5.555
3.02–32.91
19703
9033[R(int) =
0.0419]
0.0405
0.0857
0.873
5.137/-1.344
6.609
3.59–30.00
14697
6675[R(int) =
0.0286]
0.0339
0.0794
1.086
3.357/-3.063
q range (deg)
no. of data collected
no. of unique data
a
R1 [F2 > 2s(F2)]
b
wR2 (all data)
Sc (all data)
1.056
0.643/-0.377
Largest diff.
peak/hole(e A )
-3
˚
a R1(F) = RꢀF0| - |Fcꢀ/R|F0|. b wR2(F2) = [Rw(F0 - Fc2)2/[Rw(F02)2]1/2, where w = [s (F0)2 + (aP)2 + bP]-1 with P = [max(F02, 0) + 2 Fc2]/3. c S =
2
2
[R(F0 - Fc2)2/(n-p)]1/2, where n is the number of reflections and p is the number of refined parameters.
2
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The Royal Society of Chemistry 2011
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HRP2 ELISA
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A highly sensitive HRP2-based ELISA was employed for assess-
ment of parasite growth inhibition as described previously.40
Curve fitting and determination of IC50 values: Hyperbolic
concentration response curves were fitted to the data points by
nonlinear least squares as described.41
X-ray diffraction studies
Diffraction data for compounds HSe1, [Au(S2)(PPh3)],
[Au2(S2)2(l-dppee)] and [Au2(S3)2(l-dppb)] were collected at low
temperatures using an Oxford Diffraction Gemini E Ultra
diffractometer, equipped with an EOS CCD area detector and
a four-circle kappa goniometer. For the data collection the Mo
source emitting graphite-monochromated Mo-Ka radiation (l =
˚
0.71073 A) was used. Data integration, scaling and empirical
absorption correction was carried out using the CrysAlis Pro
program package.42 Diffraction data for compounds HS1 and
[Au2(Se1)2(l-dppf)] were collected at 100 K using a Nonius
KappaCCD diffractometer housed at a rotating anode (Nonius
20 C. S. K. Rajapakse, A. Martinez, B. Naoulou, A. A. Jarzecki, L. Suarez,
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1131.
˚
FR591) producing Mo-Ka-radiation (l = 0.71073 A) equipped
with a graphite monochromator. Data collection and integration
were controlled by the collect package.43 Scaling and absorption
correction were performed using SADABS.44 The structures were
solved using Direct Methods or Patterson Methods and refined by
Full-Matrix-Least-Squares against F2. The non-hydrogen atoms
were refined anisotropically and hydrogen atoms were placed
at idealised positions and refined using the riding model. All
calculations were carried out using the program Olex2.45 Impor-
tant crystallographic and refinement parameters are collected in
Table 3.
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25 J. P. Scovill, D. L. Klayman and C. F. Franchino, J. Med. Chem., 1982,
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26 J. P. Scovill, D. L. Klayman and C. F. Franchino, US 4,657,903, 1987.
27 D. Gallenkamp, E. R. T. Tiekink and F. Mohr, Phosphorus, Sulfur
Silicon Relat. Elem., 2008, 183, 1050–1056.
28 D. Gallenkamp, T. Porsch, A. Molter, E. R. T. Tiekink and F. Mohr,
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29 E. Vergara, S. Miranda, F. Mohr, E. Cerrada, E. R. T. Tiekink, P.
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30 D. Dolfen, K. Schottler, V. Seied-Mojtaba, M. A. Jakupec, B. K.
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List of abbreviations
PTA
1,3,5-triaza-7-phosphadamantane
bis(diphenylphoshino)methane
bis(diphenylphosphino)ethane
bis(diphenylphosphino)ethylene
bis(diphenylphosphino)propane
bis(diphenylphosphino)butane
bis(diphenylphosphino)ferrocene
dppm
dppe
dppee
dppp
dppb
dppf
Acknowledgements
We thank RETORTE GmbH for a generous gift of selenium metal.
A.M. gratefully acknowledges a scholarship from the University
of Wuppertal.
38 D. L. Klayman, J. P. Scovill, J. F. Bartosevich and C. J. Mason, J. Med.
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40 H. Noedl, W. H. Wernsdorfer, R. S. Miller and C. Wongsrichanalai,
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9820 | Dalton Trans., 2011, 40, 9810–9820
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The Royal Society of Chemistry 2011
©