902
Can. J. Chem. Vol. 79, 2001
ture. The mixture was heated to boiling for 20 min, which
diately turned deep orange. The reaction mixture was stirred
for 30 min with a gradual increase of temperature until room
temperature was reached. The solvent was partially removed
under reduced pressure, and subsequently ether was added
when the solution became sufficiently concentrated to in-
duce precipitation of the product. The product was filtered,
dried under vacuum for 2 h, and stored in a refrigerator,
yield 78%, mp at ~ 205°C. +FAB-MS (NBA/CHCl3) m/z: is
yielded
a
clear solution. Upon cooling,
a
yellow
microcrystalline powder was obtained, which was filtered on
a frit and washed with ether. Yields: Method A: 55% (some
loss occurs due to the limited solubility of the product in
CH2Cl2.); Method B: 78% (this was our best method);
Method C: 28% (as crystallized product), mp 295°C (dec.).
+FAB-MS (insolubility of product prevented satisfactory
spectrum to be obtained). The complex is partially soluble in
chlorinated solvents and THF, and insoluble in ether and
1
similar to 3a, ([M – Cl2]+). H NMR (CDCl3, 300 MHz,
20°C) δ: 8.05–7.90 (m, 4H, Ph), 7.60–7.40 (m, 6H, Ph), 2.05
(d, JP,H = 7.79 Hz, 4H, 2CH2), 1.81 (d, JP,H = 8.19 Hz, 6H,
2CH3). 31P NMR (300 MHz, CDCl3, 20°C) δ: 70.06 (s, no
4JP,P coupling detected, PPh2), 42.02 (s, no 4JP,P coupling de-
tected, PMe2). Anal. calcd. for C16H20Cl2P2S2Au2: C 23.92,
H 2.51; found: C 22.84, H 2.49 (some loss of Cl2 is ex-
pected). Orange needles suitable for X-ray crystallographic
studies were obtained from a concentrated CH2Cl2 solution
layered with hexane.
1
hexane. H NMR (300 MHz, CDCl3, 20°C) δ: 8.06–7.92 (m,
8H, Ph), 7.58–7.38 (m, 12H, Ph). 31P NMR (200 MHz,
CDCl3, 19°C) δ: 67.43 (s). Anal. calcd. for C24H20P2S4Au2:
C 32.32, H 2.24, S 14.33; found: C 32.92, H 2.13, S 13.86.
[AuS2P(C6H4-p-Me)2]2 (2b)
Starting from [NH4][S2P(C6H4-p-Me)2] the toluene deriva-
tive was obtained in the same manner as described in
Method A for 2a, yield 77%, mp 275°C. 1H NMR
(200 MHz, CDCl3, 20°C) δ: 7.90–7.78 (m, 8H, Ph),
7.22–7.12 (m, 8H, Ph), 2.37 (br s, 12H, 4Me). 31P NMR
(200 MHz, CDCl3, 20°C) δ: 66.62 (s). Anal. calcd. for
C28H28P2S4Au2: C 35.45, H 2.97; found: C 35.62, H 3.08.
[Au2{dppm}{S2PPh2}2]n (5)
A 50-mL Schlenk tube was charged with a solution of 2a
(0.1 g, 0.11 mmol) in CH2Cl2 (10 mL) at room temperature.
To the yellow suspension was added dppm (0.043 g, 0.11
mmol) in one portion. The initial suspension became a clear
solution after a few minutes, followed by formation of a
white precipitate that emerged after 30–40 min. The solvent
was subsequently removed under reduced pressure until a
concentrated solution was obtained. Ether was added in ex-
cess to precipitate and consolidate the solid. The product
was filtered on a frit and washed with ether. The product is a
white solid and is sparingly soluble in polar and non-polar
solvents, yield 72%, mp 227°C. 1H NMR (300 MHz, CDCl3,
20°C) δ: 8.28–8.12 (m, 8H, Ph), 7.80–7.62 (m, 12H, Ph),
7.50–7.35 (m, 8H, Ph), 7.26–7.10 (m, 12H, Ph), 4.26 (br s,
2H, PCH2P). Anal. calcd. for C49H42P4S4Au2: C 46.09,
H 3.32, S 10.04; found: C 45.07, H 3.42, S 8.83.
Au2[(CH2)2PMe2](S2PPh2) (3a)
A 50-mL Schlenk tube was charged with a solution of 2a
(75.8 mg, 0.085 mmol) and [Au(CH2)2PMe2]2 (48 mg,
0.085 mmol) in CH2Cl2 (10 mL) at room temperature. An
orange–yellow colored suspension was initially obtained
since both starting materials are sparingly soluble in CH2Cl2.
After the reaction mixture had been stirred for 10 min, a
clear orange solution was obtained, and stirring was contin-
ued for an additional 20 min, followed by filtration through
anhydrous MgSO4. The filtrate solution was concentrated by
evaporation of the solvent under reduced pressure, and ether
was added to precipitate the product, which was filtered on a
frit and air dried. Colorless blocky crystals suitable for
X-ray studies were obtained from a concentrated CH2Cl2 so-
lution layered with either ether or hexane, yield 52.3 mg
(84%), mp 208°C (dec.). +FAB-MS (NBA/CHCl3) m/z: 733
Acknowledgments
The authors acknowledge the support of the Robert A.
Welch Foundation for this work. J.M.L-de-L. also thanks the
University of La Rioja for financial support and the opportu-
nity to pursue these studies in 1998 at Texas A&M.
1
([M + 1]+). H NMR (300 MHz, CDCl3, 20°C) δ: 8.22–8.08
(m, 4H, Ph), 7.48–7.35 (m, 6H, Ph), 1.24 (d, JP,H = 13.2 Hz,
4H, 2CH2), 1.10 (d, JP,H = 12.6 Hz, 6H, 2CH3). 31P NMR
(300 MHz, CDCl3, 20°C) δ: 68.52 (d, JP,P = 11.9 Hz, PPh2),
34.78 (d, JP,P = 11.9 Hz, PMe2). Anal. calcd. for
C16H20P2S2Au2: C 26.24, H 2.75; found: C 26.32, H 2.81.
References
1. (a) R.P. Andres, J.D. Bielefeld, J.I. Henderson, D.B. Janes,
V.R. Kolagunta, C.P. Kubiak, W.J. Mahoney, and R.G.
Osifschin. Science, 273, 1690 (1996); (b) M. Antler. Gold
Bull. 16, 2 (1983); (c) L.H. Dubois and R.G. Nuzzo. Ann. Rev.
Phys. Chem. 43, 437 (1992).
2. (a) R.V. Parish and S.M. Cottrill Gold Bull. 20, 3 (1987);
(b) D.R Haynes and M.W. Whitehouse. New developments in
antiarthritic therapy. Edited by K.D. Rainsford and G.P. Velo.
Kluwer Academic Publishers, Dordrecht. 1989. Chap. 8,
pp. 207.
[Au2{(CH2)2PMe2}{S2PEt2}] (3b)
Prepared in the same fashion as 3a, but 1 was used as a
starting material instead of 2a, yield 78%. 1H NMR
(300 MHz, CDCl3, 20°C) δ: 2.30 (dq, JP,H = 7.8 Hz, 4H,
2CH2CH3), 1.60 (d, JP,H = 12.3 Hz, 6H, 2P-CH3), 1.38 (dt,
JP,H = 21.3 Hz, 6H, 2CH2CH3), 1.23 (d, JP,H = 12.3 Hz, 4H,
2P-CH2-Au). 31P NMR (300 MHz, CDCl3, 20°C) δ: 81.93
(d, JP,P = 7.9 Hz, PEt2), 34.20 (d, JP,P = 7.9 Hz, PMe2).
3. R. Lok, W.W. Weimar, and M.W. Marshall. Patent U.S
59 121 12A. U.S.A. 1999.
4. (a) W.E. van Zyl, J.M. López-de-Luzuriaga, and J.P. Fackler,
Jr. J. Mol. Struct. 516, 99 (2000); (b) M.A. Mansour, W.B.
Connick, R.J. Lachicotte, H.J. Gysling, and R. Eisenberg. J.
Am. Chem. Soc. 120, 1329 (1998).
Au2Cl2[(CH2)2PMe2][S2PPh2] (4)
A 50-mL Schlenk tube was charged with a solution of 3a
(60 mg, 0.082 mmol) in CH2Cl2 (8 mL) at room tempera-
ture. The solution was cooled to 0°C and PhI·Cl2 (26 mg,
0.095 mmol) was added in one portion. The solution imme-
© 2001 NRC Canada