1386
A.P. Shaw et al. / Journal of Organometallic Chemistry 693 (2008) 1382–1388
solvent was evaporated, the residue extracted with benzene,
and after filtration the bright yellow solution was evapo-
rated to give a yellow solid. The solid was washed with
MeOH several times and dried under vacuum (0.19 g,
was stirred for 20 min. The volume was reduced by vacuum
and the product precipitated by the addition of 35 mL of
water. The yellow solid was filtered, washed with water
(4 ꢂ 10 mL), and dried under vacuum (0.20 g, 0.27 mmol,
1
1
0.29 mmol, 58% yield). H NMR (300 MHz, CD2Cl2): d
82% yield). H NMR (400 MHz, DMSO-d6): d ꢀ13.96 (t,
ꢀ13.50 (t, RuH, JP–H = 34.3 Hz, 1H), 1.36 (s, t-Bu, 9H),
2.02–2.50 (m, Ph2PCH2CH2PPh2, 4H), 4.44 (apparent t,
Cp, apparent J = 2.0 Hz, 2H), 5.23 (apparent t, Cp, appar-
ent J = 2.0 Hz, 2H), 7.30–7.71 (m, Ar, 20H). 31P {1H}
NMR (121.5 MHz, CD2Cl2): d 91.87. Anal. Calc. for
C36H38O2P2Ru: C, 64.95; H, 5.75. Found: C, 64.65; H,
5.69%.
RuH,
JP–H = 35.0 Hz,
1H),
1.95–2.34
(m,
Ph2PCH2CH2PPh2, 4H), 4.35 (s, Cp, 2H), 5.13 (s, Cp,
2H), 7.28–7.38 (m, Ar, 12H), 7.41–7.50 (m, Ar, 4H),
7.56–7.60 (m, Ar, 2H), 7.65–7.68 (m, Ar, 1H), 7.73–7.80
(m, Ar, 6H). 31P {1H} NMR (161.9 MHz, DMSO-d6): d
90.16. Anal. Calc. for C39H38N2O2P2Ru: C, 64.19; H,
5.25; N, 3.84. Found: C, 64.09; H, 5.35; N, 3.62%.
3.7. (C5H4CO2H)Ru(dppe)I (5a)
3.10. (C5H4CO2H)Ru(S,S-CHIRAPHOS)I (5b)
A solution of 4a (0.69 g, 0.99 mmol) in 50 mL of CH2Cl2
was stirred with trimethylsilyl iodide (0.42 mL, 2.97 mmol)
for 30 min. Water (40 mL) was added and the mixture stir-
red overnight, then the volatile components were removed
by vacuum. The product was collected by filtration, washed
with 10 mL of MeOH, 10 mL of Et2O, and 4 mL of
CH2Cl2, then dried under vacuum to give 0.64 g of a
brick-red powder (0.87 mmol, 88% yield). 1H NMR
(400 MHz, DMSO-d6): d 2.68–2.85 (m, Ph2PCH2CH2PPh2,
4H), 4.18 (s, Cp, 2H), 5.19 (s, Cp, 2H), 7.07–7.84 (m, Ar,
20H), 12.22 (br, CO2H, 1H). 31P {1H} NMR (161.9
MHz, DMSO-d6): d 79.39. Anal. Calc. for C32H29IO2P2Ru:
C, 52.26; H, 3.97; I, 17.25. Found: C, 52.28; H, 3.84; I,
17.01%.
A solution of 3 (1.41 g, 1.70 mmol) and (2S,3S)-
bis(diphenylphosphino)butane (0.77 g, 1.79 mmol) in
70 mL of toluene was refluxed for 16 h. The reaction mix-
ture was loaded on a column (230–400 mesh silica,
14 cm ꢂ 2 cm diameter). Elution of phosphines with ben-
zene followed by elution of a red band with benzene/ether
(1/5) and evaporation of the solvent gave a red solid (the
ester complex). This solid was treated with trimethylsilyl
iodide (0.73 mL, 5.1 mmol) in 50 mL of CH2Cl2 for
30 min, then 15 mL of water was added and the mixture
was stirred for 20 h. Volatile components were removed
by vacuum. The product, an orange powder, was filtered
and washed with 6 mL of MeOH and 10 mL of Et2O,
then dried under vacuum (1.05 g, 1.38 mmol, 80% yield).
1H NMR (400 MHz, DMSO-d6): d 0.96–1.08 (m, CH3,
6H), 2.13–2.25 (m, CH, 1H), 3.00–3.10 (m, CH, 1H),
3.76 (s, Cp, 1H), 4.64 (s, Cp, 1H), 4.99 (s, Cp, 1H),
5.02 (s, Cp, 1H), 6.83–6.90 (m, Ar, 2H), 7.20–7.48 (m,
Ar, 14H), 7.48–7.54 (m, Ar, 2H), 7.79–7.83 (m, Ar, 2H),
12.01 (s, CO2H, 1H). 31P {1H} NMR (161.9 MHz,
DMSO-d6): AB pattern, d 78.45 (d, JP–P = 34.0 Hz),
81.72 (d, JP–P = 34.0 Hz). Anal. Calc. for C34H33IO2P2Ru:
C, 53.48; H, 4.36; I, 16.62. Found: C, 53.35; H, 4.40; I,
16.38%.
3.8. (C5H4CO2H)Ru(dppe)H (7a)
A solution of 5a (1.85 g, 2.52 mmol) and KOH (1.70 g,
30.3 mmol) in 50 mL of MeOH was refluxed for 18 h.
The color of the mixture changed from red to light yel-
low during reflux. At room temperature, benzoic acid
(4.07 g, 33.3 mmol) was added in one portion and the
mixture was stirred for 20 min. Addition of 7 mL of
water gave a yellow precipitate which was filtered and
washed twice with 10 mL of water and twice with
10 mL of Et2O. The yellow solid was dried under vacuum
(1.38 g, 2.26 mmol, 90% yield). 1H NMR (300 MHz,
DMSO-d6): d ꢀ13.93 (t, RuH, JP–H = 34.8 Hz, 1H),
1.95–2.40 (m, Ph2PCH2CH2PPh2, 4H), 4.51 (apparent t,
Cp, apparent J = 2.1 Hz, 2H), 5.19 (apparent t, Cp,
apparent J = 2.1 Hz, 2H), 7.28–7.44 (m, Ar, 16H),
7.65–7.74 (m, Ar, 4H), 11.67 (br, CO2H, 1H). 31P {1H}
NMR (161.9 MHz, DMSO-d6): d 90.20. Anal. Calc. for
C32H30O2P2Ru: C, 63.05; H, 4.96. Found: C, 62.88; H,
4.91%.
3.11. (C5H4CO2H)Ru(S,S-CHIRAPHOS)H (7b)
A solution of 5b (0.40 g, 0.52 mmol) and KOH (0.28 g,
5.0 mmol) in 15 mL of MeOH was refluxed for 6 h. At
room temperature, AcOH (0.40 mL, 7.0 mmol) was added
in one portion and the mixture was stirred for 20 min.
Addition of 15 mL of water gave a yellow precipitate which
was filtered, washed with water (3 ꢂ 5 mL), and dried
1
under vacuum (0.27 g, 0.42 mmol, 81% yield). H NMR
(400 MHz, DMSO-d6): d ꢀ13.34 (dd, RuH, J = 37.8 Hz,
J = 27.6 Hz, 1H), 0.62–0.82 (m, CH3, 6H), 1.80–1.95 (br,
CH, 2H), 4.24 (s, Cp, 1H), 4.36 (s, Cp, 1H), 4.90 (s, Cp,
1H), 4.94 (s, Cp, 1H), 7.25–7.72 (m, Ar, 20H), 11.43 (br,
CO2H, 1H). 31P {1H} NMR (161.9 MHz, DMSO-d6): AB
3.9. [(C5H4CO2)Ru(dppe)H][benzamidinium] (8a)
A solution of 5a (0.24 g, 0.33 mmol) and KOH (0.25 g,
4.40 mmol) in 15 mL of MeOH was refluxed for 20 h. At
room temperature, benzamidine hydrochloride (1.0 g,
6.39 mmol) was added in one portion and the mixture
pattern, d 92.87 (d, JP–P = 35.7 Hz), 94.70 (d, JP–P
=
35.7 Hz). Anal. Calc. for C34H34O2P2Ru: C, 64.04; H,
5.37. Found: C, 63.75; H, 5.32%.
Shaw, Anthony P.
