(
)
T.E. Muller et al.rJournal of Organometallic Chemistry 551 1998 313–330
323
¨
undissolved gold was filtered off. The solid was extracted with MeOH, the white crystals dissolved in CH2Cl2 and
Ž
.
the remaining gold 0.613 g, 3.1 mmol recovered. The CH2Cl2 solution was mixed with hexane and the volume
w
Ž
.x
reduced until a white precipitate formed which was filtered off and dried in vacuo to yield 5.737 g AuCl SMe2 . The
MeOH solution was reduced slowly to a small volume, the crystals which formed were filtered off, washed with Et2O
and CHCl3, recrystallised from MeOH–Bu2O and dried in vacuo to yield yellow crystals 1.218 g which were
Ž
.
characterised to be HAuCl4 P2Me2 SO.
[
(
)]
4.5.1. AuCl SMe2
Yield: 5.737 g, 86% relative to Au . Found: C, 8.1; H, 1.8%. Calc. for C2 H6 AuClS: C, 8.1; H, 2.0%. H NMR
Ž .
1
Ž
.
CDCl : d 2.8 s . n cmy1 1437s, 1423s, 1414s, 1384w, 1034s, 995s, 345m, 326m.
Ž
.
˜
3
max
[
]
4.5.2. HAuCl4 P2Me2 SO
Ž
.
Yield: 1.218 g, 11% relative to Au . Found: C, 9.9; H, 2.6; Au, 35.4; Cl, 25.1%. Calc. for C4 H13 AuCl4 S2O2: C,
1
13
13
Ž
.
Ž .
Ä1
4
Ž .
Ž
.
Ž .
Ž
.
9.7; H, 2.6; Au, 39.7; Cl, 28.6%. H NMR D2O : d 2.5 s . C H NMR D2O : d 40.8 s . C NMR CD3OD : d
1
1
1
13
39.3 q, J C, H 138 Hz . H MAS ECHO: d 3.0 s , 16.4 s . C H MAS: d 41.0 s . n cmy1 3000m,
Ž
Ž13
.
.
Ž .
Ä1
4
Ž .
˜
max
Ž
.
Ž
.
Ž
.
Ž
.
2915m, 1423m S–CH3 , 1325m d S–CH3 , 1181b, vs n S5O , 1027m, 939m, 907m, 717b, vs, 353vs n Au–Cl ,
323w. Raman: 3008w, 2921m, 691w, 345vs n Au–Cl , 321s Au–Cl .
Ž
.
Ž
.
(
)
( )
4.6. Synthesis of the chloro tertiary-phosphine gold I complexes
3
Ž
.
About 1.0 mmol of phosphine was dissolved in CH2Cl2 20 cm and added over a period of 5 min to a
3
w
Ž
.
x
Ž
. Ž .
magnetically-stirred solution of AuCl SMe2
0.295 g, 1.0 mmol in CH2Cl2 20 cm . The complex was
precipitated by addition of hexane, followed by removal of dimethylsulfide and CH2Cl2 in a partial vacuum. The
product was filtered off, recrystallised from CH2Cl2–hexane and dried in vacuo.
[
(
)]
4.6.1. AuCl PNp3
Yield: 91%. Found: C, 51.1; H, 2.9%. Calc. for C30 H21AuClP: C, 51.0; H, 3.2%. P H NMR CDCl3 : d 7.0
31
Ä1
4
Ž
.
1
1
3
1
3
1
3
Ž .
Ž
.
Ž
Ž1
.
.
Ž
Ž1
.
.
Ž
Ž1
.
s . H NMR CDCl3 : d 8.80 d, J H, H 8.4 Hz, 3 H , 8.08 d, J H, H 7.6 Hz, 3H , 7.99 d, J H, H 7.9
3
1
3
1
4
1
3
1
3
1
.
Ž
.
Ž1
.
Ž1
.
Ž1
.
.
.
Ž
Ž
Ž1
.
Ž1
.
Hz, 3H , 7.60 ddd, J H, H 7.9, J H, H 6.9, J H, H 1.0 Hz, 3H , 7.51 ddd, J H, H 8.4, J H, H
4
1
6.9, J H, H 1.2 Hz, 3H , 7.30 m, 3H , 7.25 m, 3H . n cmy1 337 n AuCl .
Ž1
.
Ž
.
Ž
.
˜
max
[
(
)]
4.6.2. AuCl PNp2 Ph
31
Ä1
4
Ž
.
Yield: 97%. Found: C, 51.4; H, 3.2%. Calc. for C26 H19 AuClP: C, 52.5; H, 3.2%. P H NMR CDCl3 : d 17.4
13
31
31
Ž .
Ä1
4
Ž
.
Ž
Ž1
.
.
Ž
Ž1
Ž .
.
.
Ž .
Ž
Ž1
s . C H NMR CDCl3 : d 136.4 d, J H, P 14.7 Hz , 134.8 d, J H, P 7.3 Hz , 134.0 s , 133.2 d, J H,
31
31
31
.
.
Ž
.
Ž1
P 2.4 Hz , 130.2 d, J H, P 12.2 Hz , 130.0 s , 128.5 s , 127.7 s , 126.8 d, J H, P 14.6 Hz , 125.7 d,
.
.
Ž .
Ž .
Ž
Ž1
.
.
Ž
31
31
1
3
1
Ž1
J H, P 12.2 Hz , 124.3 d, J H, P 61 Hz . H NMR CDCl3 : d 8.68 d, J H, H 8.3 Hz, 2H , 8.05 d,
.
Ž
Ž1
.
.
Ž
.
Ž
Ž1
.
.
Ž
3
1
3
1
3
1
3
1
Ž1
.
.
Ž
Ž1
.
.
Ž
Ž1
.
Ž1
.
.
J H, H 7.9 Hz, 2H , 7.96 d, J H, H 7.9 Hz, 2H , 7.68 dd, J H, H 7.9, J H, H 6.0 Hz, 2H ,
3
1
3
1
4
31
3
31
Ž
.
Ž
.
Ž1
.
Ž1
.
Ž1
.
.
Ž
Ž1
.
7.63y7.44 m, 7H , 7.35 ddd, J H, H 7.9, J H, H 6.9, J H, P 2.0 Hz, 2H , 7.12 ddd, J H, P 14.5,
3
1
4
1
J H, H 6.9, J H, H 1.2 Hz, 2H . n cmy1 331 n AuCl . mrz 594 M , 559 M–Cl
q
y
Ž1
.
Ž1
.
Ž
.
Ž
.
Ž
.
.
˜
max
[
(
)]
4.6.3. AuCl PNpPh2
Yield: 86%. Found: C, 48.3; H, 2.8%. Calc. for C22 H17 AuClP: C, 48.5; H, 3.1%. 31 P H NMR CDCl3 : 26.9 s .
Ä1
4
Ž
.
31
Ž .
13
31
31
Ä1
4
Ž
.
Ž
Ž1
C H NMR CDCl3 : d 135.4 d, J H, P 13.4 Hz , 134.4 d, J H, P 8.5 Hz , 134.1 d, J H, P 7.3 Hz ,
.
.
Ž
Ž1
.
.
Ž
Ž1
.
.
31
31
31
31
Ž
Ž1
Ž .
.
.
Ž
Ž1
.
.
Ž
Ž1
.
.
Ž
Ž1
.
133.9 d, J H, P 2.4 Hz , 133.5 d, J H, P 12.2 Hz , 132.8 d, J H, P 2.5 Hz , 130.0 d, J H, P 12.2
31
31
31
.
Ž
Ž1
.
.
Ž .
Ž .
Ž
Ž1
Ž
.
.
.
Ž
Ž1
.
P
Hz , 129.9 s , 128.7 d, J H, P 63.5 Hz , 128.4 s , 127.6 s , 126.3 d, J H, P 14.7 Hz , 125.5 d, J H,
11.0 Hz , 125.1 d, J H, P 61.0 Hz . H NMR, resolution enhanced, CDCl3 : d 8.41 td, J H, H 8.5,
31
1
3
1
.
Ž
Ž1
.
.
Ž
Ž1
.
4r5
1
3
1
4
1
3
1
4
1
Ž1
.
.
Ž
Ž1
.
Ž1
.
1
.
Ž
Ž
Ž1
.
Ž1
.
J H, H 1.0 Hz, 1H , 8.04 dd, J H, H 8.3, J H, H 1.2 Hz, 1H , 7.93 d, J H, H 8.2, J H, H 1.6
3
31
3
1
4
.
Ž
Ž1
Hz, 1H , 7.60 ddd, J H, P 13.5, J H, H 8.3, J H, H 1.4 Hz, 4H , 7.56 m, 3H , 7.47 m, 5H , 7.40 ddd,
.
Ž1
.
Ž1
.
.
.
Ž
.
Ž
3
1
3
1
4
31
3
31
3
1
4
1
Ž1
.
Ž1
.
Ž
Ž1
.
.
Ž
Ž1
.
Ž1
.
Ž1
.
J H, H 8.3, J H, H 7.2, J H, P 2.0 Hz, 1H , 7.02 ddd, J H, P 14.5, J H, H 7.2, J H, H 1.2
Hz, 1H . n cmy1 327 n AuCl . mrz 1053 M qAuPNpPh2 , 544 M , 509 M–Cl
.
q
q
y
.
.
Ž
.
Ž
.
Ž
.
˜
max
[
(
)]
4.6.4. AuCl PAn3
31
13
1
Ä1
4
Ž
.
Ž .
Ä1
4
Ž
.
Ž .
Ž
.
Yield: 72%. P H NMR CDCl3 : d y4.5 s . C H NMR CDCl3 : 134.4y122.0 s . H NMR CDCl3 : d
3
1
3
1
3
1
3
1
Ž
.
Ž
Ž1
.
.
Ž
Ž1
.
.
Ž
Ž1
Ž
.
Ž1
.
8.8 s, 3H , 8.4 d, J H, H 8.9 Hz, 6H , 8.0 d, J H, H 8.3 Hz, 6H , 7.3 dd, J H, H 8.3 Hz, J H, H 6.6
3
1
3
1
Hz, 6H , 6.9 dd, J H, H 8.9 Hz, J H, H 6.6 Hz, 6H . n cmy1 327 n AuCl . mrz 794 M , 759
q
.
Ž
Ž1
.
Ž1
.
.
.
Ž
.
˜
max
y
Ž
.
.
M–Cl