P. Singh et al. / Inorganic Chemistry Communications 13 (2010) 988–991
991
30 cm3 of ethanol was reacted with solution (added drop wise) of NaBH4 (0.14 g,
4.0 mmol) in NaOH (5%) under N2 atmosphere at room temperature (for L1) or
under refluxing (for L2). The resulting PhSeNa/ArTeNa. was treated with 4-(2-
chloroethyl)morpholine hydrochloride (0.74 g, 4.0 mmol) dissolved in 5 cm3 of
ethanol with constant stirring. The reaction mixture further stirred for 3–4 h was
poured into ice cold water (20 cm3) containing 0.2 g of NaOH. The ligand L1 or L2
was extracted into CHCl3 (5×40 cm3). The extract was washed with water
(3×50 cm3) and dried over anhydrous sodium sulphate. On evaporating off
chloroform under reduced pressure on rotary evaporator L1/L2 was obtained as
oil (L1: pale yellow; L2: white) L1: Yield (0.86 g, 80%). 1H NMR (300.13 MHz;
CDCl3; 25 °C vs. Me4Si): δ 2.44–2.46 (m, 4H, H3), 2.68 (t, 2H, 3JHH 7.5 Hz, H1), 3.02
H3), 3.42 (m, 8H, H1), 3.58 (m, 8H, H2), 3.74–3.80 (m, 16H, H4), 3.85 (s, 12H,
3
3
OCH3), 6.99 (m, 8H, JHH 8.1 Hz, ArH-m to Te), 7.97 (m, 8H, JHH 8.1 Hz, ArH-o
to Te). 13C{1H} NMR (75.47 MHz; CDCl3; 25 °C vs. Me4Si): δ 23.8 (C3), 54.6
(C1), 55.5 (C2), 59.4 (C4), 66.7 (OCH3), 104.2 (ArC-Te), 116.0 (ArC-m to Te),
140.7 (ArC-o to Te), 160.2 (ArC-p to Te). 125Te{1H} NMR (94.69 MHz; CDCl3;
25 °C vs. Me2Te): δ 652.6 (d, 1J(103Rh-125Te) 53.1 Hz).
[30] X-ray crystallography; Bruker AXS SMART Apex CCD diffractometer using Mo Ka
(0.71073 Å) radiations at 100(2) K was used. Crystal data (for detail see Table S3
in online supplementary material): (2)·C2H5OH·2H2O: Crystal system, mono-
clinic; space group, P 21/n; a=15.411(3) Å; b=26.282(5) Å; c=17.012(4) Å;
b=104.126(4); Volume [Å3]=6682.0(2); Z=2; density (calc.) [Mg m−3] 1.736;
F(000) 3430.0; index ranges: −18≤h≤18, −31≤k≤31, −20≤l≤20; absorp-
tion coeff. [mm−1] 2.149; Independent reflections (Rint.) 11445 (0.0639); Max./
min. Transmission; 0.704/0.574; data/restraints/parameters 11445/0/739; R indices
(all data): R1=0.0748; wR2=0.1182; Largest diff. peak/hole [e Å−3] 1.632/−0.977.
3
(t, 2H, JHH 7.5 Hz, H2), 3.66–3.69 (m, 4H, H4), 7.19–7.24 (m, 3H, ArH-m+ArH-p
3
to Se), 7.48 (d, 2H, JHH 6.6 Hz, ArH-o to Se). 13C{1H} NMR (75.47 MHz; CDCl3;
25 °C vs. Me4Si): δ 24.4 (C3), 53.1 (C1), 58.5 (C2), 66.6 (C4), 126.6 (ArC-p to Se),
128.8 (ArC-m to Se), 130.1 (ArC-o to Se), 132.2 (ArC-Se). 77Se{1H} NMR
(57.24 MHz; CDCl3; 25 °C vs. Me2Se): δ 279.46. L2: Yield (0.75 g, 80%). 1H NMR
´
˚
[31] Selected bond length(A): (2)·C2H5OH·2H2O: Rh(1)–Te(1) 2.6509(9), Rh(1)–
3
(300.13 MHz; CDCl3; 25 °C vs. Me4Si): δ 2.46–2.49 (m, 4H, H3), 2.78 (t, 2H, JHH
Te(2) 2.6549(8), Rh(1)–Te(3) 2.6546(9), Rh(1)–Te(4) 2.6688(8), Rh(1)–Cl(1)
2.3531(18), Rh(1)–Cl(2) 2.3645(17); bond angle(o): Cl(1)–Rh(1)–Cl(2) 178.26(7),
Cl(1)–Rh(1)–Te(1) 91.27(5), Cl(1)–Rh(1)–Te(2) 86.63(5), Cl(1)–Rh(1)–Te(3)
92.03(5), Cl(1)–Rh(1)–Te(4) 90.18(5), Cl(2)–Rh(1)–Te(1) 88.53(5), Cl(2)–Rh(1)–
Te(2) 91.66(5), Cl(2)–Rh(1)–Te(3) 88.25(5), Cl(2)–Rh(1)–Te(4) 91.53(5), Te(1)–
Rh(1)–Te(2) 92.49(3), Te(1)–Rh(1)–Te(3) 175.85(3), Te(1)–Rh(1)–Te(4) 87.94(2),
Te(2)–Rh(1)–Te(3) 90.20(2), Te(2)–Rh(1)–Te(4) 176.79(3), Te(3)–Rh(1)–Te(4)
89.54(2).
7.5 Hz, H1), 3.04 (t, 2H, 3JHH 7.5 Hz, H2), 3.68–3.71 (m, 4H, H4), 3.79 (s, 3H, OCH3),
3
3
6.76 (d, 2H, JHH 6.9 Hz, ArH-m to Te), 7.68 (d, 2H, JHH 6.9 Hz, ArH-o to Te). 13C
{1H} NMR (75.47 MHz; CDCl3; 25 °C vs. Me4Si): δ 7.8 (C3), 53.1 (C1), 55.1 (C2),
59.3 (C4), 66.9 (OCH3), 101.3 (ArC-Te), 115.0 (ArC-m to Te), 140.7 (ArC-o to Te),
159.5 (ArC-p to Te). 125Te{1H} NMR (94.69 MHz; CDCl3; 25 °C vs. Me2Te): δ 431.52.
[27] A.K. Singh, J. Sooriyakumar, S. Husebye, K.W. Tornroos, J. Organomet. Chem.
612 (2000) 46.
[28] A.K. Singh, J. Sooriyakumar, R.J. Butcher, Inorg. Chim. Acta 312 (2001) 163.
[29] General procedure for synthesis of complexes [RhCl2(L1)4] [ClO4] (1) and [RhCl2(L2)4]
[ClO4] (2)·C2H5OH·2H2O: The mixture of ethanolic solution (20 cm3) of RhCl3·3H2O
(0.053 g, 0.2 mmol) and a solution of L1/L2 (0.054/0.070 g, 0.2 mmol) made in C2H5OH
(7 cm3) was stirred for 3–4 h, followed by addition of AgClO4 (0.042 g, 0.2 mmol) in
C2H5OH (5 cm3) till itbecame orange for1 and red for 2. The AgClwas filteredoff. The
volume of filtrate was reduced to ∼7 cm3 on a rotary evaporator. The addition of
diethyl ether (15 cm3) to the concentrate gave 1 (orange) and 2 (red) as precipitate
which was filtered, washed with diethyl ether (10 cm3) and dried in vacuo. Single
crystals of 2 suitable for X-ray diffraction were obtained by slow evaporation of its
[32] General procedure for catalytic transfer hydrogenation reaction: A mixture of the
ketone (1 mmol), KOH (0.2 cm3 of a 0.2 M solution in 2-propanol) and the
catalyst complex 1/2 (0.001 mol%) was heated under reflux (80 °C) in 10 cm3 of
2-propanol for 10 h. In the course of reaction an aliquot was taken at desired time
intervals, extracted with diethyl ether, filtered through a short path of silica and
the silica was washed with diethyl ether. The combined organic filtrates were
evaporated on a rotary evaporator and analyzed by 1H NMR spectroscopy (in
CDCl3) and GC. The final conversions are determined by average of two runs of
each catalytic reaction.
[33] R. Noyori, M. Yamakawa, S. Hashiguchi, J. Org. Chem. 66 (2001) 7931.
[34] M. Yamakawa, H. Ito, R. Nayori, J. Am. Chem. Soc. 122 (2000) 1466.
[35] O. Tutusaus, C. Viñas, R. Núñez, F. Teixidor, A. Demonceau, S. Delfosse, A.F. Noels, I.
Mata, E. Molins, J. Am. Chem. Soc. 125 (2003) 11830.
[36] M. Harberhold, H. Yan, W. Milius, B. Wrackmeyer, Organometallics 19 (2000)
4289.
[37] K. Badyal, W.R. McWhinnie, J. Homer, M.C. Perry, J. Organometallic Chem. 555 (1998)
279.
[38] A. Kjekshus, T. Rakke, A.F. Andresen, Acta Chem. Scand. A 32 (1978) 209.
[39] W.Z. Biltz, Anorg. Allg. Chem. 233 (1937) 282.
solution made in a mixture (1:4) of C2H5OH and CH3CN. 1: Yield (0.230 g, 85%). ΛM
:
140.9 S cm2 mol−1. Anal. Calcd. for C48H72Cl2N4O4RhSe4.ClO4: C, 42.45; H, 5.34; N,
4.13%. Found: C, 42.49; H, 5.36; N, 4.15%. 1H NMR (300.13 MHz; CDCl3; 25 °C vs.
Me4Si): δ 2.45–2.48 (m, 16H, H3), 3.25 (m, 8H, H1), 3.49 (m, 8H, H2), 3.90 (m, 16H,
H4), 7.27–7.34 (m, 12H, ArH-m+ArH-p to Se), 8.02 (m, 8H, ArH-o to Se). 13C{1H}
NMR (75.47 MHz; CDCl3; 25 °C vs. Me4Si): δ 24.5 (C3), 55.2 (C1), 59.3 (C2), 67.2 (C4),
126.8 (ArC-p to Se), 129.3 (ArC-m to Se), 130.8 (ArC-o to Se), 134.6 (ArC-Se).
77Se{1H} NMR (57.24 MHz; CDCl3; 25 °C vs. Me2Se): δ 388.5 (d, 1J(103Rh-77Se)
46.4 Hz). 2: Yield (0.284 g, 85%). ΛM
52H80Cl2N4O8RhTe4.ClO4: C, 37.34; H, 4.82; N, 3.35%. Found: C, 37.34; H, 4.85;
N, 3.36%. 1H NMR (300.13 MHz; CD3CN; 25 °C vs. Me4Si): δ 2.46–2.50 (m, 16H,
: . Anal. Calcd. for
142.5 S cm2 mol−1
C