Phenylene-1,4- and biphenylene-4,4′-diselenolate bridged complexes of gold(I)

Article abstract of DOI:10.1139/V08-159

Homobimetallic gold-selenolate complexes of the type [(Ph ₂R)PAuSe(C₆H₄)_nSeAuP(Ph ₂R)] (3a, R = Et, n = 1; 3b, R = Et, n = 2; 5a, R = Ph, n = 1; 5b, R = Ph, n = 2) are obtained by the reaction of [Ph<

Full text of DOI:10.1139/V08-159

380
Phenylene-1,4- and biphenylene-4,4′-diselenolate
bridged complexes of gold(I)1
Deeb Taher, Nicholas J. Taylor, and John F. Corrigan
Abstract: Homobimetallic gold-selenolate complexes of the type [(Ph2R)PAuSe(C6H4)nSeAuP(Ph2R)] (3a, R = Et, n =
1; 3b, R = Et, n = 2; 5a, R = Ph, n = 1; 5b, R = Ph, n = 2) are obtained by the reaction of [Ph2RPAuCl] (1, R = Et;
4, R = Ph) with 0.5 equiv. of Me3SiSe(C6H4)nSeSiMe3 (2a, n = 1; 2b, n = 2) in good yield. Complex
[(Pr3P)AuSe(C6H4)2SeAu(PPr3)] 7b can be prepared in a two-step synthesis procedure: treatment of [AuCl(SMe2)] 6
with 0.5 equiv. of Me3SiSe(C6H4)2SeSiMe3 2b gives [(Me2S)AuSe(C6H4)2SeAu(SMe2)], which further reacts with PPr3
to afford 7b. The new gold-selenolate complexes have been characterized by multinuclear NMR (1H, 31P, 77Se) and ele-
mental analysis. The solid state structures of 3b, 5a, and 7b were determined by single X-ray structure analysis.
Key words: gold, dimer, selenolate, biphenylene, phenylene.
Résumé : La réaction des produits de formule générale [Ph2RPAuCl] (1, R = Et; 4, R = Ph) avec 0,5 équivalents de
Me3SiSe(C6H4)nSeSiMe3 (2a, n = 1; 2b, n = 2) conduit à la formation de complexes homobimétalliques sélénolate d’or
du type [(Ph2R)PAuSe(C6H4)nSeAuP(Ph2R)] (3a, R = Et, n = 1; 3b, R = Et, n = 2; 5a, R = Ph, n = 1; 5b, R = Ph, n =
2) avec de bons rendements. On peut préparer le complexe [(Pr3P)AuSe(C6H4)2Au(PPr3)] (7b) par une méthode de
synthèse en deux étapes dans laquelle le traitement du [AuCl(SMe2)] (6) avec 0,5 équivalents de Me3SiSe(C6H4)2Se-
SiMe3 (2b) conduit à la formation du [(Me2S)AuSe(C6H4)2SeAu(SMe2)] qui, par réaction subséquente avec du PPr3,
fournit le produit 7b. Les nouveaux complexes sélénolates d’or ont été caractérisés par la RMN multinucléaire (1H,
31P et 77Se) et par analyse élémentaire. Faisant appel à la diffraction des rayons X, on a déterminé les structures des
produits 3b, 5a et 7b à l’état solide.
Mots-clés : or, dimère, sélénolate, biphénylène, phénylène.
[Traduit par la Rédaction] Taher et al. 385
Introduction
selenolate salts (10, 11, 12), the coupling of stannyl
diselenolate (13), the reaction with PhSeSiMe3 (14, 15), as
well as reactions between gold(I) chloride with organic
selenolate ligands in the presence of AgSbF6 (15). They
have also been prepared by the reaction Ph3PAuN(SiMe3)2
with selenols (16).
As part of our continued interest in developing the struc-
tural chemistry of metal–selenium interactions with conju-
gated diselenolate ligands (17), we report here a simple and
efficient method for the synthesis and characterization of a
small series of dimeric gold(I) selenolate complexes incor-
porating phosphines as ligands. These represent the first
structures for gold selenolates of this type.
The coordination chemistry of Au(I) is a most important
branch of inorganic chemistry (1), and in particular there has
been considerable interest in the study of gold(I) phosphine
complexes of the type R3PAuL (L = anionic ligand) in part
because of the successful use of auranofin (a second-line,
orally administered gold drug) for the treatment of rheuma-
toid arthritis (2, 3). Recent reviews by McKeage et al. (4)
and Tiekink (5) also highlight that Et3PAuCl and other
gold(I) phosphine complexes can act as potential anti-tumor
agents. With the rapid explosion of the ligand chemistry of
the heavier chalcogen elements, it is somewhat surprising
that the chemistry of gold selenolates has been the focus of
less attention, despite the great possibilities that the com-
pounds can offer regarding their structures (6). Gold(I)
selenolates, including mononuclear gold(I) complexes of the
type [Au(SeR)(PR3)] (7, 8), have been prepared by the reac-
tion of gold(I) chloride with selenols (9), or alkali metal
Results and discussion
When RPh2PAuCl (1, R = Et; 4, R = Ph) was reacted with
0.5 equimolar amounts of 1,4-bis(trimethylsilylseleno)-
phenylene (2a) or biphenylene-4,4′-bis(trimethylsilylselenium)
Received 25 July 2008. Accepted 18 August 2008. Published on the NRC Research Press Web site at canjchem.nrc.ca on
3 December 2008.
Dedicated with thanks and admiration to Richard J. Puddephatt: a more magnanimous colleague will never be found.
D. Taher and J.F. Corrigan.2 Department of Chemistry, The University of Western Ontario, London, ON N6A 5B7, Canada.
N.J. Taylor.3 Department of Chemistry, University of Waterloo, Waterloo, ON N2L 3G1, Canada.
1This article is part of a Special Issue dedicated to Professor R. Puddephatt.
2Corresponding author (e-mail: corrigan@uwo.ca).
3Deceased.
Can. J. Chem. 87: 380–385 (2009)
doi:10.1139/V08-159
© 2008 NRC Canada

Taher et al.
381
Scheme 1.
Table 1. Selected NMR spectroscopic data for 3a, 3b, 5a, and
5b in CDCl3 and yield.
Table 2. A summary of the bond lengths and angles.
Compound
31P
77Se
Yield (%)
3a
3b
5a
5b
7b
38.9
41.4
39.9
39.6
32.5
148.6
157.0
148.2
156.6
143.7
72
75
71
73
75
Compounds
3b
5a
7b
Note: Chemical shifts are reported in ppm.
Bond lengths (Å)
a
1.88(1)
1.93(1)
1.94(1)
a′
1.88(1)
1.90(1)
1.91(1)
(2b), the digold(I) selenolate complexes [(RPh2P)AuSe-
(C6H4)nSeAu(PPh2R)] (3a, R = Et, n = 1; 3b, R = Et, n = 2;
5a, R = Ph, n = 1; 5b, R = Ph, n = 2) are formed, with the
elimination of Me3SiCl (Scheme 1). After appropriate work-
up, 3a, 3b, 5a, and 5b can be isolated in yields between 71%
and 75% as pale yellow solids.
b
2.409(1)
2.409(1)
2.271(2)
2.271(2)
2.408(1)
2.401(2)
2.264(3)
2.263(4)
2.407(1)
2.407(2)
2.274(4)
2.265(4)
b′
c
c′
Bond angles (°)
α
α′
β
105.5(3)
105.5(3)
173.47(7)
173.47(7)
103.2(4)
103.5(4)
178.95(8)
175.26(9)
102.1(4)
105.2(4)
179.6(1)
178.4(1)
Air stable 3a, 3b, 5a, and 5b are soluble in common or-
ganic solvents, including dichloromethane and chloroform.
They were characterized by 1H, 31P{1H}, and 77Se{1H}
NMR spectroscopy. The results are summarized in Table 1.
The 1H NMR spectrum of [(EtPh2P)AuSeC6H4SeAu(PPh2Et)]
3a displays, in addition to the aromatic and aliphatic reso-
nances from the phosphine ligands, a singlet for the aryl pro-
tons of the 1,4-phenylene moiety at 7.41 ppm. The 31P{1H}
NMR spectra of solutions of 3a display one singlet for the
two equivalent phosphorus atoms at 38.9 ppm with no evi-
β′
tionic complex 1,4-[{(p-CH3C6H4)3PAu}2SC6H4S{Au(P-p-
C6H4CH3)3}2][BF4]2. This also leads to short intramolecular
(3.16–3.21 Å) and intermolecular (2.97–3.16 Å) Au–Au
interactions and an infinite chain-like arrangement of the
1,4-[(Au)2SC6H4S(Au)2]2+ repeat units (18). In 5a, no signif-
icant AuLAu interactions are present, with distances
(4.45 Å) significantly longer than the sum of the van der
Waals radii (3.6 Å). A “head-to-tail” arrangement of adja-
cent Ph3P-Au fragments leads to the crystallographic repeat
observed in 5a, with only weak interactions between adja-
cent 1,4-[(Ph3P)AuSeC6H4SeAu(PPh3)] (AuLSe = 3.37 and
3.54 Å) (Fig. 2).
2
dence for satellites arising from JPSe coupling. The
77Se{1H} NMR spectrum consists of a singlet for the two
equivalent selenium atoms at 148.6 ppm. Reactions with
triphenylphosphine gold(I) chloride proceeded under similar
conditions to yield 1,4-[(Ph3P)AuSeC6H4SeAu(PPh3)] 5a.
Small, single crystals of 5a were obtained by diffusing n-
pentane onto CH2Cl2 solutions, isolated as the CH2Cl2 solvate.
The structural parameters are summarized in Table 2, and
the crystallographic details are provided in the Experimental
section (Table 3). The structure of 5a (Fig. 1) confirms the
expected, near liner coordination about the Au(I) centres
(P-Au-Se = 178.95(8)° for Au1 and 175.26(9)° for Au2).
The two Ph3PAuSe units are nearly parallel (deviation =
1.1°), with each rotated out of the plane defined by the C6
phenylene spacer by 99°.
The 1H NMR spectra of biphenylene bridged 4,4′-
[(EtPh2P)AuSe(C6H4)2SeAu(PPh2Et)]
3b
and
4,4′-
[(Ph3P)AuSe(C6H4)2SeAu(PPh3)] 5b display two doublets at
7.68 and 7.24 ppm, and 7.73 and 7.24 ppm, respectively, for
the equivalent protons of the biphenylene rings. Consistent
with the proposed structures, the 31P{1H} NMR spectrum
displays one signal for the equivalent phosphorus atoms
(41.4 ppm for 3b and 39.6 for 5b), and the 77Se{1H} NMR
spectrum shows the expected equivalence of the
AuSe(C6H4)2SeAu groups with one signal for each complex
Schmidbaur and co-workers (18) reported recently that
treatment of phenylene-1,4-diol with [{(p-CH3C6H4)3PAu}3O][BF4]
in a 1:1 ratio leads to the formation of the tetragold dica-
© 2008 NRC Canada

382
Can. J. Chem. Vol. 87, 2009
Table 3. Crystallographic data summary for complexes 3b, 5a, and 7b.
3b
5a
7b
Empirical formula
C40H38Au2P2Se2
C43H36Au2Cl2P2Se2
C30H50Au2P2Se2
Wavelength
Temp (K)
Radiation type
Space group
a (Å)
b (Å)
c (Å)
α (°)
0.710 73
150
Mo Kα
P2(1)/c
19.045(2)
15.0517(6)
15.583(1)
295
150
P2(1)/n
P-1
13.214(1)
9.9501(9)
14.366(1)
8.4172(3)
12.6614(5)
17.4832(8)
110.580(2)
99.271(3)
95.174(3)
10.875
β (°)
γ (°)
95.403(3)
113.930(1)
µ (mm–1)
Diffractometer
F(000)
9.840
Bruker APEX
1068
9.200
Nonius Kappa CCD
2336
Nonius Kappa CCD
972
θ range (°)
Index ranges
2.00–26.37
–13 ≤ h ≤ 16
–12 ≤ h ≤ 11
–17 ≤ k ≤ 16
8661
2.34–27.55
–24 ≤ h ≤ 24
–12 ≤ k ≤ 19
–20 ≤ l ≤ 20
14974
2.48–27.70
–10 ≤ h ≤ 10
–16 ≤ k ≤ 16
–22 ≤ l ≤ 22
14635
No. of reflns collected
No. of ind. reflns
3843
9362
7776
R indices [(I) > 2σ(I)]
R1 = 0.0481
R1 = 0.0657
R1 = 0.0883
wR2 = 0.0591
R1 = 0.0954
wR2 = 0.0654
wR2 = 0.1521
R1 = 0.1612
wR2 = 0.1976
wR2 = 0.2332
R1 = 0.1055
wR2 = 0.2485
R indices (all data)
Refinement method
Refinement software
Full-matrix least-squares on F2
SHELXTL
Note: R1 = Σ**Fo* – *Fc**/ Σ *Fo*; wR2 = {Σ [w(Fo – Fc2)2/ Σ [wFo ]2]1/2
.
2
2
Fig. 1. A perspective view of the molecular structure of 1,4-
[(Ph3P)AuSeC6H4SeAu(PPh3)] 5a. Thermal ellipsoids are drawn
at the 40% probability level.
Fig. 2. The packing of 1,4-[(Ph3P)AuSeC6H4SeAu(PPh3)] 5a in
the crystal (hydrogen atoms omitted).
(3b: 157.0; 5b: 156.6 ppm). The 3lP{lH} NMR data are simi-
lar to those reported for related (triphenylphosphine)gold(I)
thiolate and selenolate complexes (12, 19, 20, 21). The 77Se
NMR shifts of the biphenylene linked 3b and 5b resonate at
higher field than their 1,4-phenylene linked counterparts 3a
and 5a.
Crystals of 4,4′-[(EtPh2P)AuSe(C6H4)2SeAu(PPh2Et)] 3b
were obtained from layering CH2Cl2 solutions with pentane.
A summary of bond lengths and angles is provided in Ta-
ble 2. Molecular 3b resides about a crystallographic inver-
sion centre (monoclinic space group P21/n), which bisects
the atoms labelled C4-C4A (Fig. 3). The two C6 rings are
thus crystallographically co-planar and thus similar to the re-
ported 4,4′-[Cl(Bu3P)2PdSe(C6H4)2SePd(PBu3)2Cl] (17) and
4,4′-[(Cy3P)AuS(C6H4)2SAu(PCy3)] (18). The Au centres in
3b deviate from linearity (173.47(7)) sightly more than was
oberved in 5a. There are no significant intermolecular inter-
actions.
Treatment of (Me2S)AuCl in THF solution with
Me3SiSe(C6H4)2SeSiMe3 (2b) at –78 °C produced an insolu-
ble material (“(Me2S)AuSe(C6H4)2SeAu(SMe2)”) which can
be used without isolation for the preparation of
trialkylphosphine stabilized (R3P)AuSe(C6H4)2SeAu(PR3).
The addition of two equivalents of PPr3 to a suspension of
(Me2S)AuSe(C6H4)2SeAu(SMe2) (at –78 °C) resulted in a
clear solution from which weakly diffracting single crystals
© 2008 NRC Canada

Taher et al.
383
Fig. 3. A perspective view of the molecular structure of 4,4′-
[(EtPh2P)AuSe(C6H4)2SeAu(PPh2Et)] 3b. Thermal ellipsoids are
drawn at the 40% probability level.
Fig. 5. A projection along the inter-ring C–C bond in 4,4′-
[(Pr3P)AuSe(C6H4)2SeAu(PPr3)] 7b illlustrating the orientation of
the phenylene rings and the Au-Se-P moeities (propyl chains
omitted).
Fig. 4. The molecular structure of 4,4′-[(Pr3P)AuSe(C6H4)2SeAu(PPr3)]
7b. Thermal ellipsoids are drawn at the 40% probability level.
which would allow for the preparation of coordination poly-
mers (23) of the type [AuPPh2(CH2)xPh2PAuSe(C6H4)2Se]n.
We are currently developing these avenues of research.
Experimental section
All syntheses were carried out under an atmosphere of
high-purity dried nitrogen using standard double-manifold
Schlenk line techniques and nitrogen-filled gloveboxes.
Solvents were dried and collected using an MBraun MB-SP
Series solvent purification system. Chloroform-d was dried
and distilled over P2O5. NMR spectra [1H (399.763 MHz),
13C{1H} (100.522 MHz), 77Se{1H} (76.217 MHz)] were re-
of 4,4′-[(Pr3P)AuSe(C6H4)2SeAu(PPr3)] 7b could be iso-
1
lated. H NMR spectra for 7b display the expected signals
1
for the equivalent propyl groups at 1.80, 1.58, 1.02 ppm
with the aromatic resonances at 7.65 and 7.28 ppm, and in
the 31P{1H} NMR spectrum the equivalent phosphorus units
gives rise to single signal at 32.5 ppm. The 77Se{1H} shows
corded on a Varian Inova 400 NMR spectrometer. H and
13C NMR chemical shifts were referenced internally to
SiMe4 using the residual proton and carbon signal of the
deuterated solvent, respectively. 77Se {1H} spectra were ref-
erenced to external standards C6H5SeSiMe3 at +85.6 ppm,
relative to Me2Se at 0 ppm. Elemental analyses were per-
formed by Guelph Chemical Laboratories (Guelph, Canada).
Crystals of 3b and 7b were mounted immersed in cooled
mineral oil and placed in a cold stream of N2 during data
collection. X-ray structural analyses were carried out on
Bruker AXS (3b) and Enraf-Nonius Kappa CCD (5a and
7b) single-crystal X-ray diffractometers. Data were cor-
rected for Lorentz and polarization effects. The SHELXTL
(G.M. Sheldrick, Madison, Wisconsin, USA) program pack-
age was used to solve (direct methods, Au, Se, and P) and
refine the structures. The weighting scheme employed was
a
singlet at 143.7 ppm. Attempts to prepare 4,4′-
[(EtPh2PAuSe(C6H4)2SeAu(PPh2Et)] 3b and 4,4′-
[(Ph3PAuSe(C6H4)2SeAu(PPh3)] 5b from (“(Me2S)AuSe-
(C6H4)2SeAu(SMe2)”) via the addition of PPh2Et were un-
successful, as the suspended precipitate did not dissolve with
the addition of the larger, less basic phosphine ligand in a
variety of common organic solvents. Similarly, attempts to
prepare 4,4′-[(Pr3P)AuSe(C6H4)2SeAu(PPr3)] 7b from 4,4′-
Me3SiSe(C6H4)2SeSiMe3 2b Pr3PAu-Cl led to only poor
yields of 7b.
X-ray diffraction analysis of single crystals of 7b illustrate
that the molecular geometry in the solid state is markedly
different than that oberved for 3b (Fig. 4). Unlike the planar
C6-C6 structure observed in 3b, the two phenylene rings in
7b are rotated such that there is a 35.9° angle between them,
similar to what was reported in 4,4′-[{(p-CH3C6H4)3PAuS-
(C6H4)2S{Au(P-p-C6H4CH3)3}2]+ (40.3°). Unlike in 3b, the
P-Au-Se moieties asymmetrically lie on the same side of the
biphenylene spacer, with a 42.4° angle between the two
Se-Au-P vectors (Fig. 5). The Au-Se and Au-P distances are,
however, similar to those oberved in 3b and 5a (Table 2).
In summary, the facile preparation of 3, 5, and 7b from li-
gated Au-Cl and silylated selenium reagents has led to the
first examples of dinuclear AuSe-spacer-SeAu. The strate-
gies employed herein lend themselves to facile adaptation
using didentate ligands (e.g., [ClAuPPh2(CH2)xPh2PAuCl]),
2
of the form w = 1/[σ2(Fo ) + (aP)2 + bP] (a, b = refined vari-
2
2
ables, P = 1/3 max(Fo , 0) + 2/3 Fc ). All non-hydrogen at-
oms, with the exception of disordered carbon centers, were
refined with anisotropic thermal parameters. Hydrogen
atoms were included as riding on their respective carbon at-
oms. The structures solved and refined without complica-
tions, with the following exceptions: In 3b, a solvent
moleceule of crystallization (CH2Cl2) was refined as disor-
dered over two sites with restrained geometries; in 7b, many
of the carbon atoms of the propyl chains were disordered
over two sites. A satisfactory model with 50:50 occupancy
was refined using mild restraints (SADI command). All non-
hydrogen atoms, with the exception of disordered carbon
centres, were refined with anisotropic thermal parameters.
© 2008 NRC Canada

384
Can. J. Chem. Vol. 87, 2009
Hydrogen atoms were included as riding on their respective
carbon atoms.4
77Se{1H} δ: 156.6. Anal. for C48H38Au2P2Se2 (1228.62):
found: C 46.54, H 2.99; calcd.: C 46.92, H 3.12.
Synthesis of Pr3PAuSe(C6H4)2SeAuPPr3 (7b)
Materials
[AuCl(SMe2)] (65 mg, 0.221 mmol) was added in one
portion to 4,4′-(C6H4SeSiMe3)2 (51 mg, 0.111 mmol) in
tetrahydrofuran (30 mL) at –78 °C and warmed to RT after
15 min. After 2 h of stirring at RT, a yellow suspension
formed. The reaction mixture was again cooled to –78 °C,
and 0.43 mL of PPr3 (35.4 mg, 0.221 mol) was added in one
portion to the reaction mixture. After 2 h of stirring at RT,
all volatiles were removed in vacuo from the clear yellow
solution, and the residue obtained was washed with n-
pentane. Crystallization from n-pentane/dichloromethane
(8:1) gave colorless crystals of 7b in 75% yield (79 mg,
0.083 mmol). 1H NMR (CDCl3) δ: 7.65 (d, 4 H, JHH = 8 Hz,
C6H4), 7.23 (d, 4 H, JHH = 8 Hz, C6H4), 1.80 (m, 12 H,
CH2CH2CH3), 1.58 (m, 12 H, CH2CH2CH3), 1.02 (m, 18H,
CH2CH2CH3). 131P{1H} δ: 32.5. 77Se{1H} δ: 143.7.
Phenylene-1,4-bis(trimethylsilylselenium) and biphenyl-
ene-4,4′-bis(trimethylsilylselenium) (17), [AuCl(SMe2)] (22),
and R3PAuCl (23) were synthesized according to literature
procedures.
Synthesis of EtPh2PAuSeC6H4SeAuPPh2Et (3a)
EtPh2PAuCl (220.7 mg, 0.494 mmol) was added in one
portion to 1,4-C6H4(SeSiMe3)2 (94.0 mg, 0.247 mmol) in
tetrahydrofuran (30 mL) at –78 °C and warmed to room
temperature (RT) after 15 min. After 2 h of stirring at RT, all
volatiles were removed in vacuo, and the residue obtained
was washed with n-pentane. Crystallization from n-
pentane/dichloromethane (8:1) gave yellow crystals of 3a in
1
72% yield (188 mg, 0.178 mmol). H NMR (CDCl3) δ: 7.65
(m, 12 H, C5H4), 7.46 (m, 8 H, C5H4), 7.41 (s, 4 H,, C6H4),
2.44 (dq, 4 H, JHH = 8 Hz, JHP = 16 Hz, CH2), 1.23 (dt, 6 H,
JHH = 8 Hz, JHP = 20 Hz, CH2). 131P{1H} δ: 38.9. 77Se{1H}
δ: 148.6. Anal. for C34H34Au2P2Se2 (1056.43): found: C
37.75, H 3.43; calcd.: C 38.65, H 3.24.
Acknowledgements
We gratefully acknowledge the financial support of the
Natural Sciences and Engineering Research Council
(NSERC) of Canada. The University of Western Ontario and
the Canada Foundation for Innovation are thanked for equip-
ment funding. DT thanks Tafila Technical University (Jor-
dan) for travel support to Canada.
Synthesis of EtPh2PAuSe(C6H4)2SeAuPPh2Et (3b)
One hundred mg of 4,4′-(C6H4SeSiMe3)2 (0.219 mmol)
was reacted with 196 mg (0.438 mmol) of EtPh2PAuCl as
described for the preparation of 3a (above). After appropri-
ate work-up, 3b was isolated as yellow crystals in 75% yield
1
References
(186 mg, 0.164 mmol). H NMR (CDCl3) δ: 7.68 (d, 4 H,
JHH = 8 Hz, C6H4), 7.65 (m, 12 H, C5H4), 7.45 (m, 8 H,
1. H.G. Raubenheimer and S. Cronje. In Gold, progress in chem-
istry, biochemistry and technology. Edited by H. Schmidbaur.
Wiley, Chichester, NY, USA. 1999. p. 557.
2. C.F. Shaw III. Chem. Rev. 99, 2589 (1999).
3. S.L. Best and P.J. Sadler. Gold Bull. 29, 2987 (1996).
4. M.J. McKeage, L. Maharaj, and S.J. Berners-Price. Coord.
Chem. Rev. 232, 127 (2002).
C5H4), 7.24 (d, 4 H, JHH = 8 Hz, C6H4), 2.45 (dq, 4 H, JHH
8 Hz, JHP = 20 Hz, CH2), 1.23 (dt, 6 H, JHH = 8 Hz, JHP
=
=
20 Hz, CH2). 131P{1H} δ: 41.4. 77Se{1H} δ: 157.0. Anal. for
C40H38Au2P2Se2 (1132.52): found: C 42.18, H 3.36; calcd.:
C 42.42, H 3.38.
5. E.R.T. Tiekink. Crit. Rev. Oncol/Hematol. 42, 225 (2002).
6. S. Canales, O. Crespo, M.C. Gimeno, P.G. Jones, and A.
Laguna,. Inorg. Chem. 43, 7234 (2004).
7. P.G. Jones and C. Thöne. Chem. Ber. 123, 1975 (1990).
8. W. Eikens, C. Kienitz, P.G. Jones, and C. Thöne. J. Chem.
Soc. Dalton Trans. 83 (1994).
9. (a) R.J. Puddephatt and P.J. Thompson. J. Organomet. Chem.
117, 396 (1976); (b) S. Canales, O. Crespo, M.-C.Gimeno,
P.G. Jones, A. Laguna, and P. Romero. J. Chem. Dalton Trans.
4525 (2003).
Synthesis of Ph3PAuSeC6H4SeAuPPh3 (5a)
One hundred mg of 1,4-C6H4(SeSiMe3)2 (0.263 mmol)
was reacted with 260 mg (0.526 mmol) of Ph3PAuCl as de-
scribed for the preparation of 3a (above). After appropriate
work-up, 3b was isolated as a yellow solid in 71% yield
1
(216 mg, 0.187 mmol). H NMR (CDCl3) δ: 7.47 (m, 30 H,
C6H5), 7.42 (s, 4 H, C6H4). 131P{1H} δ: 39.9. 77Se{1H} δ:
148.2. Anal. for C42H34Au2P2Se2 (1152.52): found: C 43.49,
H 2.93; calcd.: C 43.77, H 2.97.
10. A. Laromaine, F. Teixidor, R. Kivekäs, R. Sillanpää, M. Arca,
V. Lippolis, E. Crespo, and C. Viñas. J. Chem. Soc. Dalton
Trans. 5240 (2006).
Synthesis of Ph3PAuSe(C6H4)2SeAuPPh3 (5b)
One hundred mg of 4,4′-(C6H4SeSiMe3)2 (0.219 mmol)
was reacted with 217 mg (0.438 mmol) of Ph3PAuCl as de-
scribed for the preparation of 3a (above). After appropriate
work-up, 3b was isolated as yellow solid in 73% yield
11. P.J. Bonasia, D.E. Cindelberger, and J. Amold. Inorg. Chem.
32, 5126 (1993).
12. I. Wagner and W.-W. du Mont,. J. Organomet. Chem. 395, C23
(1990).
13. E. Cerrada, S. Elipe, M. Laguna, F. Lahoz, and A. Moreno.
Synth. Met. 102, 1759 (1999).
1
(196 mg, 0.160 mmol). H NMR (CDCl3) δ: 7.73 (d, 4 H,
JHH = 8 Hz, C6H4), 7.53 (m, 18 H, C6H5), 7.43 (m, 12 H,
C6H5), 7.24 (d, 4 H, JHH = 8 Hz, C6H4). 131P{1H} δ: 39.6.
4 Supplementary data for this article are available on the journal Web site (canjchem.nrc.ca) or may be purchased from the Depository of
Unpublished Data, Document Delivery, CISTI, National Research Council Canada, Ottawa, ON K1A 0R6, Canada. DUD 3861. For more
information on obtaining material refer to cisti-icist.nrc-cnrc.gc.ca/cms/unpub_e.shtml. CCDC 696168–696170 contain the crystallographic
data for this manuscript. These data can be obtained, free of charge, via www.ccdc.cam.ac.uk/conts/retrieving.html (Or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax +44 1223 336033; or deposit@ccdc.cam.ac.uk).
© 2008 NRC Canada

Taher et al.
385
14. S. Canales, O. Crespo, M.C. Gimeno, P.G. Jones, and A.
Laguna. Inorg. Chem. 43, 7234 (2004).
19. P.G. Jones and C. Thöne. Chem. Ber. 123, 1975 (1990).
20. P.G. Jones and C. Thöne. Chem. Ber. 124, 2725 (1991).
15. W. Eikens, C. Kienitz, P.G. Jones, and C. Thöne. J. Chem.
21. P.G. Jones and C. Thöne. Inorg. Chim. Acru, 181, 291 (1991).
22. M.-C. Brandys, M.C. Jennings, and R.J. Puddephatt. J. Chem.
Soc. Dalton Trans. 4601 (2000).
23. A.A. Isab, M.B. Fettouhi, S. Ahmad, and L. Ouahab. Polyhe-
dron, 22, 1349 (2003).
Soc. Dalton Trans. 83 (2004).
16. P.J. Bonasia, D.E. Cindelberger, and J. Arnold. Inorg. Chem.
32, 5126 (1993).
17. A.I. Wallbank, M.J. Brown, C. Nitschke, and J.F. Corrigan.
Organometallics, 23, 5648 (2004).
18. H. Ehlich, A. Schier, and H. Schmidbaur. Inorg. Chem. 41,
3721 (2002).
© 2008 NRC Canada