8
N. ARSLAN
(aromatic C-H), 1438 (P-Ph), 1060 (O-P) cmꢃ1; Anal. for 7.00–7.74 (m, 17H, P(C6H5)2þ-NCHCHN-þ–CHPh), 5.67
C24H24N2OPCl (422.66 g/mol): calcd. C 68.20, H 5.72, N (br, 1H, -CHPh), 5.39 (s, 6H, aromatic protons of benzene),
4.72 (br, 2H, NCH2), 3.82 (br, 3H, -CH3N); 13C NMR
6.62; found C 68.07, H 5.56, N 6.46%.
(100.6 MHz, CDCl3, ppm): d 38.15 (CH3N), 53.51 (NCH2),
77.32 (br, -CHOP), 90.39 (s, aromatic carbons of benzene),
Synthesis of [3-[(2R)-2-(f[dichloro(g6-p-cymene)ruthenium]-
123.62, 124.38, 126.81, 128.51,129.30 (–NCHCHN– and o-,
diphenyl phosphanylgoxy)-2-phenylethyl]-1-methyl-1H-imi-
3
m-, p-carbons of –CHPh), 131.54 (d, J31P–13C ¼ 11.1 Hz, m-
dazol-3-ium chloride], (3)
P(C6H5)2), 131.71 (p-P(C6H5)2), 133.72 (d, 2J31P–13C ¼ 13.1 o-
[Ru(g6-p-cymene)(m-Cl)Cl]2 (0.072 g, 0.118 mmol) and
P(C6H5)2)), 137.37 (-(CH3)NCHN–), (not observed, i-carbon
[(Ph2P)-C12H14N2O]Cl, 2 (0.1 g, 0.235 mmol) were dissolved
of –CHPh), (not observed, i-P(C6H5)2); assignment was based
in dry CH2Cl2 (25 ml) under argon atmosphere and stirred
1
1
on the H-13C HETCOR, DEPT and H-1H COSY spectra;
for 24 h at room temperature. The volume was concentrated
to ca. 1–2 mL under reduced pressure and addition of pet-
roleum ether (20 ml) gave the corresponding ruthenium (II)
complex as a red solid. The product was collected by filtra-
31P-f Hg NMR (162.0 MHz, CDCl3, ppm): d 121.18 (s,
1
OPPh2); IR: t 3058 (aromatic C-H), 1435 (P-Ph), 1016 (O-P)
cmꢃ1; Anal. for C30H30N2OPRuCl3 (672.98 g/mol): calcd. C
53.54, H 4.49, N 4.16; found C 53.49, H 4.32, N 4.10%.
tion and dried in vacuo. Yield: 150 mg, 88%; M.p.:
20
177–79 ꢁC [a]D
¼
þ34.6ꢁ (c 1, CHCl3); 1H NMR
Synthesis of [3-[(2R)-2-f[(dichloro(î5–pentamethylcyclo
pentadienyl)iridium)diphenyl phosphanyl]oxyg-2-phenyl-
ethyl]-1-methyl-1H-imidazol-3-ium chloride], (5)
(400.1 MHz, CDCl3, ppm): d 9.38 (s, 1H, -(CH3)NCHN-),
6.81–7.77 (m, 17H, P(C6H5)2þ-NCHCHN-þ–CHPh),
5.47–5.50 (m, 1H, -CHOP), 5.45 (d, J ¼ 6.0 Hz 2H, aromatic
protons of p-cymene), 5.38 (s, 1H, aromatic protons of p-
cymene), 5.01 (d, J ¼ 5.2 Hz, 1H, aromatic protons of p-cym-
ene), 4.70 (br, 2H, NCH2), 3.88 (s, 3H, CH3N), 2.52 (m, 1H,
–CH- of p-cymene), 1.91 (s, 3H, CH3Ph of p-cymene), 1.20
(d, J ¼ 7.2 Hz, 3H, CH3)2CHPh of p-cymene), 1.03 (d,
J ¼ 6.8 Hz, 3H, CH3)2CHPh of p-cymene); 13C NMR
(100.6 MHz, CDCl3, ppm): d 17.49 (CH3Ph of p-cymene),
21.00, 22.23 ((CH3)2CHPh of p-cymene), 30.12 (–CH- of p-
cymene), 36.02 (CH3N), 56.67 (NCH2), 77.31 (br, CHOP),
86.56 (s, aromatic carbons of p-cymene), 88.88 (s, aromatic
carbons of p-cymene), 89.43 (s, aromatic carbons of p-cym-
ene), 93.29 (s, aromatic carbons of p-cymene), 96.54, 110.35
(quaternary carbons of p-cymene), 123.60, 124.33,
Ir(g5-C5Me5)(l-Cl)Cl]2 (0.094 g, 0.118 mmol) and [(Ph2P)-
C12H14N2O]Cl, 2 (0.100 g, 0.235 mmol) were dissolved in
dry CH2Cl2 (25 ml) under argon atmosphere and stirred for
24 h at room temperature. The volume was concentrated to
ca. 1–2 mL under reduced pressure and addition of petrol-
eum ether (20 ml) gave the corresponding Ir(III) complex as
an orange microcrystalline solid. The product was collected
by filtration and dried in vacuo. Yield: 180 mg, 93%; M.p.:
20
131–133 ꢁC [a]D
¼ þ46.9ꢁ (c 1, CHCl3); 1H NMR
(400.1 MHz, CDCl3, ppm): d 9.08 (s, 1H, -(CH3)NCHN-),
6.85–7.72 (m, 17H, P(C6H5)2þ-NCHCHN-þ–CHPh), 5.67
(br, 1H, -CHOP), 4.72 (br, 2H, NCH2), 3.83 (s, 3H, CH3N),
1.35 (s, 15H, CH3 of Cp*(C5Me5); 13C NMR (100.6 MHz,
CDCl3, ppm): d 8.21 (C5Me5), 36.93 (CH3N), 54.80 (NCH2),
76.93 (br, CHOP), 94.00 (d, J ¼ 3.0 Hz, C5Me5), 122.77,
123.60 (–NCHCHN–), 126.30, 128.19, 128.41 (o-, m-, p-car-
bons of –CHPh), 128.05 (d, J ¼ 8.0 Hz, m-P(C6H5)2), 131.86
(s, p-P(C6H5)2), 132.72 (d, J ¼ 12.1 Hz o-P(C6H5)2), 135.86,
(-(CH3)NCHN–) 138.36 (i-carbon of –CHPh) (not observed,
126.35,127.88, 128.52 (–NCHCHN– and o-, m-, p-carbons of
3
–CHPh), 131.67 (p-P(C6H5)2), 132.59 (d, J31P–13C
¼
2
11.1 Hz, m-P(C6H5)2), 134.05 (d, J31P–13C ¼ 11.1, o-
P(C6H5)2), 135.88 (-(CH3)NCHN–), (not observed i-carbon
of –CHPh), (not observed, i-P(C6H5)2); assignment was
based on the 1H-13C HETCOR, DEPT and 1H-1H COSY
spectra; 31P-f Hg NMR (162.0 MHz, CDCl3, ppm): d 123.69
1
1
i-P(C6H5)2); assignment was based on the H-13C HETCOR,
1
DEPT and 1H-1H COSY spectra; 31P-f Hg NMR
(s, OPPh2); IR: t 3056 (aromatic C-H), 2960 (aliphatic
C–H), 1435 (P-Ph), 1016 (O-P) cmꢃ1
;
Anal. for
(162.0 MHz, CDCl3, ppm): d 93.17 (s, OPPh2); IR: t 3056
(aromatic C-H), 2962, 2919 (aliphatic C–H), 1436 (P-Ph),
1015 (O-P) cmꢃ1; Anal. for C34H39N2OPIrCl3 (821.24 g/
mol): calcd. C 49.72, H 4.78, N 3.41; found C 49.62, H 4.61,
N 3.33%.
C34H38N2OPRuCl3 (729.09 g/mol): calcd. C 56.01, H 5.25, N
3.84; found C 55.94, H 5.18, N 3.74%.
Synthesis of [3-[(2R)-2-(f[dichloro(g6-benzene)ruthenio]di-
phenylphosphanylgoxy)-2-phenylethyl]-1-methyl-1H-imida-
zol-3-ium chloride], (4)
Conclusions
[Ru(g6-benzene)(m-Cl)Cl]2 (0.059 g, 0.118 mmol) and
[(Ph2P)-C13H16N2O2]Cl, 2 (0.100 g, 0.235 mmol) were dis-
solved in dry CH2Cl2 (25 ml) under argon atmosphere and
stirred for 24 h at room temperature. The volume was concen-
trated to ca. 1–2 mL under reduced pressure and addition of
petroleum ether (20 ml) gave the corresponding ruthenium
(II) complex as a red solid. The product was collected by fil-
In conclusion, we have developed efficient Ruthenium (II)
and Iridium (III) complexes of inexpensive and easy-to-pre-
pare phosphinite ligand based on an ionic liquid. We have
found that these complexes are efficient homogeneous cata-
lytic systems that can be readily implemented and lead to
secondary alcohols. High conversion and moderate to good
enantioselectivity were obtained in the catalytic reaction.
tration and dried in vacuo. Yield: 140 mg, 89%; M.p.:
20
125–127 ꢁC [a]D
¼
þ29.3ꢁ (c 1, CHCl3); 1H NMR Furthermore, while originally developed as a potential alter-
(400.1 MHz, CDCl3, ppm): d 9.14 (br, 1H, -(CH3)NCHN-), native to modular-designed ligands in the literature, this