J. Bravo, S. García-Fontán et al.
FULL PAPER
tospec M LSIMS (FAB+) system with 3-nitrobenzyl alcohol as ma-
trix. Microanalyses were carried out with a Fisons EA-1108 appa-
ratus. Merck silica gel 60 (0.040–0.063 mm) was used for column
chromatography.
0.72 g (42%). C104H96Cl4O10P8Ru2 (2097.61): calcd. C 59.55, H
4.61; found C 59.20, H 4.63. H NMR (CDCl3): δ = 3.68 (m, 4 H,
1
CH2, L), 3.73 [m, 4 H, CH2, L(O)], 4.17 [m, 4 H, CH2, L(O)], 4.49
(m, 4 H, CH2, L), 6.80–8.00 (m, 80 H, Ph) ppm. 31P{1H} NMR
(CDCl3): δ = 32.5 [s, (P=O), L(O)], 138.3 [t, J = 46 Hz, P, L(O)],
159.0 (d, J = 46 Hz, 2P, L) ppm. FAB+/MS: m/z (calculated for the
most abundant isotopes) 1617 [M+ – Cl – L(O)], 1580 [M+ – 2Cl –
L(O)], 1013 [RuClLL(O)]+.
Synthesis of [Ru2(µ-Cl)3(DMSO)3Cl(L)] (1): A solution of L
(2.0 mL, 0.56 mmol) in toluene was added to a solution of
[RuCl2(DMSO)4] (0.5 g, 1.03 mmol) in toluene (20 mL). The solu-
tion was heated under reflux for 1/2 h, cooled to room temperature
and concentrated under vacuum. The residue was treated with
EtOH to give a yellow solid, which was washed with EtOH and
dried under vacuum. Yield: 0.40 g (77%). C32H42Cl4O5P2Ru2S3
(108.77): calcd. C 38.10, H 4.20, S 9.54; found C 37.97, H 4.19, S
9.50. 1H NMR (CDCl3): δ = 3.04 (s, 6 H, DMSO), 3.12 (s, 6 H,
DMSO), 3.43 (s, 6 H, DMSO), 3.72 (m, 2 H, CH2), 4.26 (m, 2 H,
CH2), 7.29 (m, 12 H, Ph), 7.49 (m, 4 H, Ph), 7.78 (m, 4 H, Ph).
31P{1H} NMR (CDCl3): δ = 158.2 (s). IR (KBr): ν(SO) 1093 (s)
cm–1. FAB+/MS: m/z (calculated for the most abundant isotopes)
Synthesis of [Ru2(µ-Cl)2Cl2(L)2{PPh2(OEt)}2] (4): PPh2(OEt)
(0.05 mL, 0.24 mmol) was added to a solution of compound 2
(0.150 g, 0.12 mmol) in toluene (20 mL). The mixture was heated
under reflux for 1 h and the solvent was removed under vacuum.
Addition of Et2O gave an orange-yellow precipitate and this was
filtered off, washed with Et2O and dried under vacuum. Yield:
0.15 g (75%). C80H78Cl4O6P6Ru2 (1665.27): calcd. C 57.70, H 4.72;
1
found C 57.53, H 4.71. H NMR (CDCl3): δ = 1.22 (t, J = 7 Hz,
6 H, CH3), 3.50 (m, 4 H, OCH2), 3.86 (m, 4 H, CH2), 4.31 (m, 4
H, CH2), 6.50–7.90 (m, 60 H, Ph) ppm. 31P{1H} NMR (CDCl3): δ
= 136.3 (t, J = 46 Hz, P, LЈ), 159.7 (d, J = 46 Hz, 2P, L) ppm.
FAB+/MS: m/z (calculated for the most abundant isotopes) 1631
(M+ – Cl), 1436 (M+ – LЈ), 1401 (M+ – LЈ – Cl), 832 [RuCl2-
LLЈ]+, 797 [RuClLLЈ]+.
= 1010, (M+), 975 (M+ – Cl), 932 (M+ – DMSO), 776 (M+
3DMSO), 741 (M+ – 3DMSO – Cl), 602 [RuCl2L]+.
–
Synthesis of [Ru2(µ-Cl)3(DMSO)Cl(L)2] (2): Method (a): A solution
of L (1.8 mL, 0.50 mmol) in toluene was added to a solution of 1
(0.50 g, 0.49 mmol) in toluene (20 mL). The solution was heated
under reflux for 1/2 h and then cooled to room temperature. The
solvent was removed under vacuum and EtOH was added to the
oily residue. The resulting yellow precipitate was filtered off,
washed with EtOH and dried under vacuum. Yield: 0.43 g (68%).
Method (b): A solution of L (4.0 mL, 1.14 mmol) in toluene was
added to a solution of [RuCl2(DMSO)4] (0.5 g, 1.03 mmol) in tolu-
ene (20 mL). The reaction mixture was heated under reflux for 1 h
and then cooled to room temperature. The solvent was removed
under vacuum and EtOH was added to the oily residue. The re-
sulting yellow precipitate was filtered off, washed with EtOH and
dried under vacuum. Yield: 0.39 g (59%). C54H54Cl4O5P4Ru2S
(1282.92): calcd. C 50.55, H 4.24, S 2.50; found C 50.32, H 4.26, S
2.55. 1H NMR (CDCl3) (intensity ratio 1:4 cisoid/transoid isomers):
δ = 2.54 (s, 3 H, CH3ЈSO, transoid), 2.87 (s, 3 H, CH3ЈЈSO,
transoid), 3.22 (s, 6 H, DMSO, cisoid), 3.57–4.13 [m, (5 H, CH2,
transoid + 5 H, CH2, cisoid)], 4.33 [m, (1 H, CH2, transoid + 1 H,
CH2, cisoid)], 4.50 (m, 1 H, CH2, cisoid), 4.59 (m, 1 H, CH2, cisoid),
4.76 (m, 1 H, CH2, transoid), 4.90 (m, 1 H, CH2, transoid), 6.80–
8.30 [m, (40 H, Ph, cisoid + 40 H, Ph, transoid)] ppm. 31P{1H}
NMR (CDCl3): δ = 146.4 (s, cisoid), 148.3 (q, JAB = 44 Hz,
transoid), 151.9 (d, JAX = 55 Hz), 156.9 (s, cisoid), 160.7 (d, J =
55 Hz, transoid) ppm. C54H54Cl4O5P4Ru2S: calcd. C 50.55, H 4.24,
S 2.50; found C 49.82, H 4.28, S 2.67. FAB+/MS: m/z (calculated
for the most abundant isotopes) 1284 (M+), 1249 (M+ – Cl), 1206
(M+ – DMSO). X-ray quality crystals were obtained by slow evapo-
ration of a CH2Cl2/Et2O (1:10 v/v) solution.
Synthesis of [Ru2(µ-Cl)3(L)2{PPh(OEt)2}2]Cl (5): PPh(OEt)2
(0.07 mL, 0.24 mmol) was added to a solution of compound 2
(0.150 g, 0.12 mmol) in toluene (20 mL). The mixture was heated
under reflux for 1.5 h and the solvent was removed under vacuum.
Addition of Et2O gave a yellow precipitate and this was filtered off,
washed with Et2O and dried under vacuum. Yield: 0.13 g (67%).
C72H78Cl4O8P6Ru2 (1601.18): calcd. C 54.01, H 4.91; found C
1
53.81, H 4.88. H NMR (CDCl3): δ = 0.83 (t, 6 H, J = 7 Hz, CH3,
transoid), 0.97 (t, 6 H, J = 7 Hz, CH3, transoid), 1.25 (m, 12 H,
CH3, cisoid), 3.50–3.90 [m, 16 H, CH2 (L + LЈ), transoid], 4.01 [m,
8 H, CH2 (LЈ), cisoid], 4.26 [m, 4 H, CH2, (L)], 4.51 [m, 4 H, CH2,
(L)], 6.40–8.00 [m, (50 H, Ph, cisoid) + (50 H, Ph, transoid)] ppm.
31P{1H} NMR (CDCl3): δ = 149.6 [tapparent, Japp = 48 Hz, 2P (L),
transoid], 151.7 [d, J = 53 Hz, 4P (L), cisoid], 153.0 [tapparent, Japp
= 48 Hz, 2P (L), transoid], 156.1 [tapparent, Japp = 53 Hz, 2P (LЈ),
transoid], 158.2 [t, J = 53 Hz, 2P (LЈ), cisoid] ppm. FAB+/MS m/z
(calculated for the most abundant isotopes) 1567 (M+), 1530 (M+
–
Cl), 765 [RuClLLЈ]+. X-ray quality crystals were obtained by slow
evaporation of a CH2Cl2/Et2O (1:10 v/v) solution.
Synthesis of [RuCl2L{P(OEt)3}2] (6): P(OEt)3 (0.08 mL, 0.48 mmol)
was added to a solution of compound 2 (0.150 g, 0.12 mmol) in
toluene (20 mL). The mixture was heated under reflux for 1 h and
the solvent was removed under vacuum. Addition of Et2O gave a
pale yellow precipitate and this was filtered off, washed with Et2O
and dried under vacuum. Yield: 0.14 g (62%). C38H54Cl2O8P4Ru
1
(934.71): calcd. C 48.83, H 5.82; found C 49.05, H 5.85. H NMR
(CDCl3): δ = 0.90 (t, J = 7 Hz, 9 H, CH3), 1.22 (t, J = 7 Hz, 9 H,
CH3), 3.26 [m, 3 H, CH2 (LЈ)], 3.43 [m, 3 H, CH2 (LЈ) + 1 H, CH2
(L)], 3.98 [m, 1 H, CH2 (L)], 4.23 [m, 3 H, CH2 (LЈ)], 4.40 [m, 1
H, CH2 (L)], 4.46 [m, 3 H, CH2 (LЈ)], 5.67 [m, 1 H, CH2 (L)] ppm.
Synthesis of [Ru2(µ-Cl)2Cl2(L)2{L(O)}2] (3): Method (a): A solution
of compound 2 (0.150 g, 0.12 mmol) in toluene (20 mL) was added
to a solution of L (0.75 mL, 0.26 mmol) in toluene and the mixture
was heated under reflux for 1 h, cooled to room temperature and
the solvent removed under vacuum. Et2O was added to the residue
and the resulting yellow solid was filtered off, washed with Et2O
and dried under vacuum. Yield: 0.18 g (92%). Method (b): A mix-
ture of [RuCl2(DMSO)4] (0.5 g, 1.03 mmol) and a solution of L
(7.5 mL, 2.14 mmol) in toluene (20 mL) was heated under reflux
for 2 h with stirring. The solution was cooled to room temperature
and the solvent was removed under vacuum to give an oily residue.
Et2O (5 mL) was added and the resulting yellow solid was filtered
off. Compounds 7 and 8 were obtained from the filtrate (see below).
The solid was washed with Et2O and dried under vacuum. Yield:
31P{1H}NMR (CDCl3): δ = 97.8 (ddd, Jcis = 24, 48 Hz, Jtrans
=
544 Hz, P1), 122.0 (ddd, Jcis = 46, 64 Hz, Jtrans = 544 Hz, P4), 129.8
(ddd, Jcis = 47, 48, 64 Hz, P2), 150.7 (ddd, Jcis = 24, 46, 47 Hz,
P3) ppm. FAB+/MS: m/z (calculated for the most abundant iso-
topes) 899 (M+ – Cl), 733 [M+ – Cl – P(OEt)3]. X-ray quality crys-
tals were obtained by slow evaporation of a CH2Cl2/Et2O (1:10 v/
v) solution.
Synthesis of [RuCl2(L)(Ph2POPPh2)] (7) and [RuCl(CO)(L)-
(PPh2OCH2)] (8): From the ether solution obtained during the syn-
thesis of compound 3 [Method (b), see above], the solvent was re-
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Eur. J. Inorg. Chem. 2006, 3028–3040