852
C. Bonaccorsi et al. / Tetrahedron: Asymmetry 14 (2003) 845–854
under reflux for 10 h. Toluene was evaporated and the
resulting yellow oil was recrystallised from CH2Cl2/tol-
uene. Yield: 0.43 g (78%). [h]2D0 +51.6 0.1 (c 1.04,
and stirred for 15 min. As the complex decomposed
during crystallisation from CH2Cl2/hexane, it was char-
acterised in solution (see Section 2). 1H NMR (250
MHz, CD2Cl2): l 8.82 (d, 1H, JP,H=9.5 Hz, NꢀCH),
8.60 (s, 1H, NꢀCH), 8.0–6.0 (m, 28H, arom.). 31P NMR
(101 MHz, CD2Cl2, 273 K): l 68 (br, 1P), 46 (br, 1P),
−144.4 (septet, 1P, JP,F=714 Hz, PF6) (see also Table
1).
1
CHCl3). H NMR (250 MHz, CDCl3): l 8.30 (d, 2H,
HCꢀN, JP,H=3.4 Hz), 7.6–7.2 (m, 24H, arom.), 2.95
(m, 2H, N-CH), 1.21–1.67 (m, 8H, CH2). 31P NMR
(101 MHz, CDCl3): l −10.2 (s, 2P). MS (EI): m/z 930
(M+, 3), 785 (M+−Ph, 46), 424 (M+−2PPh, 100). IR
(KBr, cm−1): 1605 (s, wCꢀN), 1329 (s, CF3), 1166 (s,
CF3), 1132 (s, CF3), 599 (s, CF3).
4.6. [RuCl(OEt2)(1b)]PF6, 6b
4.3. trans-[RuCl2((S,S)-1b)], 2b
Complex 2b (18 mg, 0.015 mmol) was dissolved in
CD2Cl2 (1 mL) in an NMR tube fitted with a Young
valve under an atmosphere of purified nitrogen in a
glove box. After addition of (Et3O)PF6 (8 mg, 0.032
mmol, 2 equiv.), the reaction was monitored by 31P
NMR spectroscopy. After 12 h complete conversion
was observed. As the complex decomposed during crys-
tallisation from CH2Cl2/hexane, it was characterised in
[RuCl2(PPh3)3] (382 mg, 0.401 mmol, 1 equiv.) was
added to a solution of 1b (374 mg, 0.401 mmol) in
toluene and the resulting solution was heated under
reflux for 10 h. After evaporation of toluene, the result-
ing red solid was recrystallised from CH2Cl2/hexane.
1
Yield: 0.38 g (86%). [h]2D0 −189 1 (c 0.25, CHCl3). H
1
NMR (300 MHz, CDCl3): l 8.91 (d, 2H, HCꢀN,
solution. H NMR (250 MHz, CD2Cl2, 300 K): l 9.37
JP,H=8.37 Hz), 7.71–6.70 (m, 24H, arom.), 4.15 (d, 2H,
(d, 1H, HCꢀN, JP,H=10.0 Hz, 6b, 63%), 8.92 (br, 1H,
HCꢀN, 6b, 63%), 8.24 (s, 2H, HCꢀN, 7b, 37%). 31P
NMR (101 MHz, CD2Cl2, 300 K): l 56 (br, 1P, 6b,
63%), 50 (br, 2P, 7b, 37%), 38 (br, 1P, 6b, 63%), −143.2
(septet, 1P, JP,F=714 Hz, PF6). 31P NMR (CD2Cl2, 263
K): l 56.0 (d, 1P, JP,P%=29.3 Hz, 6b, 63%), 50.0 (s, 2P,
7b, 37%), 38.4 (d, 1P, JP,P%=29.3, 6b, 63%), −143.2
(septet, 1P, JP,F=714 Hz, PF6).
N-CH, JH,H%=8.1 Hz), 2.75 (d, 2H, NCH-CHH%,
JH,H%=10.7 Hz), 2.12 (m, 2H, CH2), 1.99 (m, 2H, CH2),
1.48 (m, 2H, CH2). 31P NMR (121 MHz, CDCl3): l
49.54 (s, 2P). 19F NMR (282 MHz, CDCl3): l −63.45 (s,
6F), −63.61 (s, 6F). MS (MALDI): m/z 1102 (M+, 30),
1067 (M+−Cl, 2), 1031 (M+−2Cl, 100), 885 (M+−2Cl−
Ph, 2). IR (CsI, cm−1): 1606 (m, wCꢀN), 1330 (s, CF3),
1172 (s, CF3), 1128 (s, CF3), 602 (s, CF3), 313 (w,
RuꢁCl). Anal. calcd for C48H36Cl2F12N2P2Ru: C, 52.28;
H, 3.29; N, 2.54. Found: C, 52.40; H, 3.48; N, 2.35%.
In an alternative route, [RuCl2(PPh3)3] was added to a
dichloromethane solution of 1b and the resulting solu-
tion was stirred at room temperature for 10 h. In
addition to 2b (80%), cis-[RuCl2((S,S)-1b)] (3b) (20%)
was also obtained. 31P NMR (CDCl3): l 81.4 (d, 1P,
JP,P%=37.7 Hz), 45.9 (d, 1P, JP,P%=37.7 Hz).
4.7. [RuCl(h1-O3SCF3)(1b)], 8b
Complex 2b (85 mg, 0.077 mmol) was dissolved in
CH2Cl2 and CF3SO3Si(CH3)3 (0.014 mL, 0.077 mmol)
was added dropwise at 0°C. The red solution was
stirred for 3 h at room temperature and then the
solvent was evaporated to give a red solid. Yield: 70 mg
1
(85%). H NMR (200 MHz, CDCl3): l 9.23 (d, 1H,
HCꢀN, JP,H=9.2 Hz), 8.92 (d, 1H, HCꢀN, JP,H=9.2
4.4. [RuCl(OH2)(1b)]BArF, 5bBArF
Hz), 7.80–6.20 (m, 24H, arom.), 4.62 (m, 1H, N-CH),
4.20 (m, 1H, N-CH), 3.06 (d, 1H, NCH-CHH%, JH,H%
=
NaB(4-CF3-C6H4)4 (NaBArF) (100 mg, 0.11 mmol, 1
equiv.) was added to a solution (5 mL) of 2b (122 mg,
0.11 mmol) in dichloromethane. The red solution was
stirred for 10 h at room temperature. After filtration
over Celite, the solvent was evaporated, and the brown
solid was recrystallised from CH2Cl2/hexane. Yield:
9.0 Hz), 2.67 (d, 1H, NCH-CHH%, JH,H%=9.0 Hz), 2.14
(m, 2H, CH2), 1.90 (m, H, CHH%), 1.65 (m, H, CHH%),
1.43 (m, 2H, CH2). 31P NMR (81 MHz, CDCl3): l 49.6
(d, 1P, JP,P%=26.9 Hz), 48.9 (d, 1P, JP,P%=26.9 Hz). 19F
NMR (188 MHz, CDCl3): l −63.3 (s, 3F, 1b-CF3),
−63.74 (s, 6F, 1b-CF3), −63.75 (s, 3F, 1b-CF3), −79.7 (s,
3F, RuꢁOSO2CF3). MS (MALDI): m/z 1067 (M+−
CF3SO3, 2), 1031 (M+−CF3SO3−Cl, 100), 885 (M+−
CF3SO3−Cl−Ph, 3). The crystals contain 1 molecule
CH2Cl2 per 9b, as determined by 1H NMR spec-
troscopy. Anal. calcd for C48H36Cl2F12N2P2Ru·CH2Cl2:
C, 46.15; H, 2.94; N, 2.15. Found: C, 46.62; H, 3.37; N,
2.16%.
1
0.164 g (77%). H NMR (250 MHz, CDCl3): l 8.77 (d,
1H, HCꢀN, JP,H=9.9 Hz), 8.64 (s, 1H, HCꢀN), 7.60–
6.60 (m, 36H, arom.), 4.39 (m, 2H, N-CH), 2.45–2.30
(m, 2H, N-CH), 1.7 (m, 2H, CH2), 1.2 (m, 4H, CH2).
31P NMR (101 MHz, CDCl3): l 65.5 (d, 1P, JP,P%=30.3
Hz), 47.2 (d, 1P, JP,P%=30.3 Hz). MS (MALDI): m/z
1067 (M+−H2O, 2), 1031 (M+−H2O−Cl, 100), 885 (M+−
H2O−Cl−Ph, 2). MS (ESI): m/z 1107.9 ([M+Na]+, 32),
1067.2 (M+−H2O, 100). IR (KBr, cm−1): 1610 (m, wCꢀN),
(s, CF3), 1208.4 (s, CF3), 1139 (s, CF3), 685 (s, CF3).
Anal. calcd for C80H50BClF36N2OP2Ru: C, 49.31; H,
2.59; N, 1.44. Found: C, 49.34; H, 2.70; N, 1.61%.
4.8. [RuCl(OH2)(1b)](O3SCF3), 5bO3SCF3
Water (3.2 mL, 18 mmol, 1 equiv.) was added to a
1
CDCl3 solution of 8b (20 mg, 18 mmol). The H, 31P,
and 19F NMR spectra of the reaction solution, recorded
immediately after the addition of water, indicated the
presence of 5b%% (75%) and 5b%% (15%) along with unre-
acted 8b (10%). The species distribution did not change
with time even in the presence of an excess of water
4.5. [RuCl(OEt2)(1a)]PF6, 6a
Complex 2a (30 mg, 36 mmol) and (Et3O)PF6 (9 mg, 36
mmol) were solved in dry CD2Cl2 over molecular sieves