F.v.v. Ch e´ rioux et al. / Polyhedron 22 (2003) 543Á
/548
547
i
ml of technical EtOH. When the complex is completely
dissolved, a solution of 0.6 mmol of the thiol (p-
thiocresol, 75 mg; 2-mercaptoethanol, 47 mg; p-mer-
captophenol, 76 mg) in 5 ml of EtOH is added drop-wise
to the hot solution. The resulting mixture is refluxed in
EtOH for 3 h. After cooling to 20 8C, the red solution is
filtered, and the solvent is removed under reduced
pressure. The oil obtained is purified by column
chromatography (silica gel, CH Cl /EtOH 5:1, R close
3.6. [Ru (p-CH Ã
/
C H Ã
/
Pr) (SÃ
/
C H Ã
/
OH) ]Cl
2
3
6
4
2
2
4 3
(3b)
1
IR (KBr): n˜ /
ꢁ3405 (OH). H NMR (200 MHz,
CD OD) d (ppm): 5.67 (d, Jꢁ
/
3
/
5.9 Hz, 2H; H Ã
/
Ar),
3
3
3
5.48 (d, Jꢁ
4H; H ÃAr), 3.86 (t, Jꢁ
2.84 (sept, Jꢁ
Hz, 6H; SÃCH2Ã
6.6 Hz, 6H; (CH ) CH), 1.29 (d, Jꢁ
/
5.9 Hz, 2H; H Ã
/
Ar), 5.42 (d, Jꢁ
6.1 Hz, 6H; OÃ
6.6 Hz, 2H; (CH ) CH), 2.64 (t, Jꢁ6.1
/5.9 Hz,
3
/
/
/
CH Ã
/CH2),
2
3
3
/
/
3
2
3
/
/
CH ), 2.19 (6H, s; CH ), 1.32 (d, Jꢁ
/
2
2
f
2
3
3
to 0.8). Compounds 2, 3 and 4 are isolated by evapora-
tion of the solvent as redÁorange microcrystalline
powders in quantitative yields, except in the case of
/
6.6 Hz, 6H;
3
2
ꢀ
/
(CH ) CH). MS (ESI): m/z: 703 [Mꢀ
for C H ClO Ru S (737.41): C, 42.35; H, 5.88.
Found: C, 42.19; H, 5.69%.
/
H ]. Anal. Calc.
3
2
2
6
43
3
2 3
[
Ru(C H )Cl ] as starting complex (yield: 80%).
6
6
2 2
3
.2. [Ru (C H ) (SÃ
/
C H Ã
/
p-CH ) ]Cl (2a)
2
6
6 2
6
4 3 3
3
.7. [Ru (C (CH ) ) (SÃ
/
C H Ã
/
OH) ]Cl (3c)
2
6
3 6 2
2
4 3
1
H NMR (200 MHz, CDCl ): d (ppm)ꢁ
/
7.72 (d,
8.1 Hz, 6H; H Ã
benzene), 2.38 (s, 9H; CH ). MS
3
1
3
3
IR (KBr): n˜ /
ꢁ3405 (OH). H NMR (200 MHz,
/
Jꢁ
/
8.1 Hz, 6H; H Ã
/
Ar), 7.21(d, Jꢁ
/
/
3
CD OD) d (ppm): 3.66 (t, Jꢁ
CH
/
6.1 Hz, 6H; OÃ
/
CH2Ã
/
3
Ar), 5.41 (s, 12H; RuÃ
ESI) m/z: 729 [Mꢀ
C H ClRu S (763.41): C, 51.92; H, 4.36. Found: C,
/
3
3
ꢀ
2
), 2.50 (s, Jꢁ
/
6.1 Hz, 6H; SÃCH CH ), 1.59
/
2
Ã
/
2
(
/H ]. Anal. Calc. for
ꢀ
(36H, s; CH ). MS (ESI): m/z: 759 [Mꢀ
/
H ]. Anal.
3
3
3
33
2 3
Calc. for C H ClO Ru S (793.51): C, 45.41; H, 6.48.
Found: C, 45.29; H, 6.24%.
3
0
51
3
2 3
5
1.65; H, 4.51%.
i
3
.3. [Ru (p-CH Ã
/
C H Ã
/
Pr) (SÃ
/
C H Ã
/p-CH ) ]Cl
3 3
2
3
6
4
2
6
4
(
2b)
3
.8. [Ru (C H ) (SÃ
/
C H Ã
/
p-OH) ]Cl (4a)
3
2
6
6 2
6
4
1
3
1
3430 (OH). H NMR (200 MHz,
H NMR (200 MHz, CDCl ) d (ppm): 7.73 (d, Jꢁ
/
3
3
IR (KBr): n˜ /
ꢁ
/
3
8
5
.1 Hz, 6H; H Ã
/
Ar), 7.17 (d, Jꢁ
6.0 Hz, 2H; H ÃAr), 5.18 (d, Jꢁ
6.0 Hz, 2H; H Ã
Ar), 2.36 (9H, s; CH ), 1.94 (sept,
/
8.1 Hz, 6H; H Ã
/
Ar),
CD OD) d (ppm): 7.72 (d, Jꢁ
/
8.1 Hz, 6H; H Ã
Ar), 5.41 (s, 12H; RuÃ
benzene), C NMR (50 MHz, [d ]DMSO) d (ppm):
/
Ar),
3
3
3
3
.31 (d, Jꢁ
H; H ÃAr), 5.11 (d, Jꢁ
5.7 Hz, 2H; H Ã
/
/
/
5.7 Hz,
7
.21(d, Jꢁ
/
8.1 Hz, 6H; H Ã
/
/
3
1
3
2
3
/
/
/
Ar), 5.06 (d,
6
Jꢁ
/
/
3
115.9, 125.4 (RuÃ
(ESI) m/z: 736 [Mꢀ
C H ClO Ru S (769.32): C, 46.84; H, 3.54. Found:
/
benzene), 132.3, 133.6, 144.5. MS
3
3
ꢀ
Jꢁ
Jꢁ
CH ) CH). MS (ESI) m/z: 842 [Mꢀ
/
6.8 Hz, 2H; (CH ) CH), 1.60 (6H, s; CH ), 0.89 (d,
3
2
3
/H ]. Anal. Calc. for
3
/
6.8 Hz, 6H; (CH ) CH), 0.78 (d, Jꢁ
/
6.8 Hz, 6H;
H ]. Anal. Calc.
3
2
3
0
27
3
2 3
ꢀ
(
/
3
2
C, 46.92; H, 3.63%.
for C H ClRu S (875.62): C, 56.24; H, 5.64. Found:
C, 56.38; H, 5.86%.
4
1
49
2 3
i
3
.9. [Ru (p-CH Ã
/
C H Ã
/
Pr) (SÃ
/
C H Ã
/
p-OH) ]Cl
2
3
6
4
2
6
4 3
(
4b)
3
.4. [Ru (C (CH ) ) (SÃ
/
C H Ã
/
p-CH ) ]Cl (2c)
2
6
3 6 2
6
4 3 3
1
1
3
IR (KBr): n˜ /
ꢁ3438 (OH). H NMR (200 MHz,
/
H NMR (200 MHz, CDCl ) d (ppm): 7.77 (d, Jꢁ
/
3
3
3
[d ]DMSO) d (ppm): 9.85 (3H, s; OH), 7.68 (d, Jꢁ
/
8
2
8
.0 Hz, 6H; H Ã
/
Ar), 7.16 (d, Jꢁ
/
8.0 Hz, 6H; H Ã/Ar),
6
3
8
.6 Hz, 6H; H Ã
/
Ar), 6.80 (d, Jꢁ
4.9 Hz, 2H; H ÃAr), 5.38 (d, Jꢁ
4.9 Hz, 2H; H Ã
/
8.6 Hz, 6H; H Ã
/
Ar),
.39 (9H, s; CH ), 1.71 (36H, s; CH ). MS (ESI) m/z:
ꢀ
3
3
3
3
5.58 (d, Jꢁ
/
/
/
4.9 Hz,
97 [MꢀH ]. Anal. Calc. for C H ClRu S (931.72):
/
45 57 2 3
3
2
3
H; H ÃAr), 5.26 (d, Jꢁ
/
/
/
Ar), 5.21 (d,
Ar), 1.93 (sept, Jꢁ6.8 Hz, 2H;
6.8 Hz, 6H;
C, 58.01; H, 6.17. Found: C, 57.76; H, 5.98%.
3
Jꢁ
/
4.9 Hz, 2H; H Ã
/
/
3
(
CH ) CH), 1.55 (6H, s; CH ), 0.85 (d, Jꢁ
/
3
2
3
3
13
3
.5. [Ru (C H ) (SÃ
/
C H Ã
/
OH) ]Cl (3a)
3
(CH ) CH), 0.74 (d, Jꢁ
/
6.8 Hz, 6H; (CH ) CH).
NMR (50 MHz, [d ]DMSO) d
((CH ) CH), 21.61 ((CH ) CH), 30.71 (CH ), 70.12
C
(ppm): 21.31
2
6
6 2
2
4
3 2
3 2
6
1
3405 (OH). H NMR (200 MHz,
IR (KBr): n˜ /
ꢁ
/
3
2
3 2
3
CD OD) d (ppm): 5.69 (s, 12H; RuÃ
/
benzene) 3.66 (t,
((CH ) CH), 106.895 (C Ã
/
Ar), 115.73 (C Ã
/
Ar), 125.20
3
3 2
3
3
Jꢁ
H; SÃ
Calc. for C H ClO Ru S (625.2): C, 34.58; H, 4.35.
/
6.1 Hz, 6H; OÃ
/
CH2Ã
/
CH ), 2.50 (t, Jꢁ
/
6.1 Hz,
(C Ã
MS (ESI) m/z: 847 [Mꢀ
C H ClO Ru S (881.54): C, 51.77; H, 4.92. Found:
/
Ar), 127.36 (C Ã
/
Ar), 134.10 (C Ã
/
Ar), 158.1 (C(O).
2
ꢀ
ꢀ
6
/
CH2ÃCH ). MS (ESI): m/z: 591 [Mꢀ
/
/
H ]. Anal.
/
H ]. Anal. Calc. for
2
1
8
27
3
2
3
38 43
3
2 3
Found: C, 34.71; H, 4.51%.
C, 51.86; H, 4.98%.