892
Y.S. Varshavsky, T.G. Cherkasova / Journal of Organometallic Chemistry 692 (2007) 887–893
3
.3.2. (Me NH ) [RhCl (DMF)] carbonylation
2
acknowledged. Authors thank M.V. Borisova for the pH
2 2
5
As the salt is insoluble in DMF, even at heating, carbon-
ylation was carried out in the presence of excess PPh3
4 mol per Rh). PPh (1.46 g, 5.6 mmol) was added to the
measurements and V.V. Yastrebov for his encouraging
support.
(
3
suspension
of
(Me NH ) [RhCl (DMF)]
(0.623 g,
2
2 2
5
References
1
.4 mmol) in DMF (10 ml). The reaction vessel was
immersed into a preheated oil bath. After 40 min reflux,
the initial solid disappeared. On cooling the yellow solution
to the room temperature, a yellow crystalline solid formed.
Ethanol (20 ml) was added to complete sedimentation, the
product was separated by filtration, washed by ethanol,
and identified as trans-Rh(CO)Cl(PPh ) by IR(m(CO)
[1] J. Chatt, B.L. Shaw, Chem. Ind. (1960) 931.
[
[
[
[
[
2] J. Tsuji, K. Ohno, Tetrahedron Lett. (1965) 3969.
3] R.H. Prince, K.A. Raspin, Chem. Commun. 6 (1966) 156.
4] D. Evans, J.A. Osborn, G. Wilkinson, Inorg. Synth. 11 (1968) 99.
5] M.J. Clear, W.P. Griffith, J. Chem. Soc (A) (1969) 372.
6] R. Colton, R.H. Farthing, J.A. Knapp, Aust. J. Chem 23 (1970)
1351.
3
2
ꢀ
1
31
31
[
7] Rusina, A.A. Vl cˇ ek, Nature 206 (1965) 295.
1
978 cm
in CHCl ) and P NMR (d P 29.2 ppm,
3
1
[8] Yu.S. Varshavskii, T.G. Cherkasova, Zh. Neorg. Khim. (Russ.) 12
1967) 1709;
J(PRh) 125.9 Hz in CDCl ). Yield 0.90 g (93%).
3
(
Yu.S. Varshavskii, T.G. Cherkasova, Russ. J. Inorg. Chem 12 (1967)
899.
3
with BaCO3
.3.3. Carbonylation of commercial RhCl Æ nH O pretreated
3 2
[9] Yu.S. Varshavskii, N.N. Knyazeva, T.G. Cherkasova, N.V. Ivannik-
ova, T.I. Ionina, Zh. Neorg. Khim. (Russ.) 15 (1970) 715;
Yu.S. Varshavskii, N.N. Knyazeva, T.G. Cherkasova, N.V. Ivannik-
ova, T.I. Ionina, Russ. J. Inorg. Chem 15 (1970) 367.
10] Yu.S. Varshavskii, T.G. Cherkasova, N.A. Buzina, N.N. Knyazeva,
T.I. Ionina, Zh. Neorg. Khim. (Russ.) 15 (1970) 2294;
Yu.S. Varshavskii, T.G. Cherkasova, N.A. Buzina, N.N. Knyazeva,
T.I. Ionina, Russ. J. Inorg. Chem. 15 (1970) 367.
11] Yu.S. Varshavsky, N.V. Kiseleva, T.G. Cherkasova, N.A. Buzina, J.
Organomet. Chem. 31 (1971) 119.
12] I.B. Bondarenko, N.A. Buzina, Yu.S. Varshavskii, M.I. Gel’fman,
V.V. Razumovskii, T.G. Cherkasova, Zh. Neorg. Khim. (Russ.) 16
(1971) 3071;
Commercial preparation of RhCl Æ nH O (0.40 g,
3
2
1
.4 mmol) was dissolved in DMF (10 ml), and BaCO3
0.5 g, 2.5 mmol) was added. After stirring the suspension
for 1 h, the solid was filtered off, a fresh portion of BaCO3
0.5 g) was added and the suspension was left overnight.
(
[
(
The solid was filtered off again and the carbonylation pro-
cedure was carried out in the standard manner.
[
[
3
.3.4. Carbonylation of RhCl(PPh3)
3
To the preheated (153 °C) DMF (25 ml) a mixture of
RhCl(PPh3)3 (0.68 g, 0.73 mmol) and PPh3 (0.39 g,
.5 mmol) was added. After heating for 5 min, the intensity
I.B. Bondarenko, N.A. Buzina, Yu.S. Varshavskii, M.I. Gel’fman,
V.V. Razumovskii, T.G. Cherkasova, Russ. J. Inorg. Chem. 16
1
(
1971) 1029.
ꢀ1
of carbonyl stretching band at 1977 cm came up to com-
plete carbonylation value. On cooling the reaction mixture
to the room temperature a yellow crystalline solid precipi-
tated. Ethanol (25 ml) was added to complete the precipita-
tion. The product was isolated by filtration, washed by
ethanol and diethyl ether, and dried in vacuo. It was iden-
[
[
13] Yu.S. Varshavskii, T.G. Cherkasova, O.A. Osipov, N.P. Bednyagina,
A.D. Garnovskii, R.I. Ogloblina, G.K. Mitina, G.N. Lipunova, Zh.
Neorg. Khim. (Russ.) 17 (1972) 1401;
Yu.S. Varshavskii, T.G. Cherkasova, O.A. Osipov, N.P. Bednyagina,
A.D. Garnovskii, R.I. Ogloblina, G.K. Mitina, G.N. Lipunova,
Russ. J. Inorg. Chem 17 (1972) 1372.
14] L.Yu. Ukhin, Yu.A. Shwezov, Izv. AN SSSR, Ser. Khim. 7 (1972)
1653.
3
1
tified as trans-Rh(CO)Cl(PPh ) by IR and P NMR (see
3
2
Section 3.3.2). Yield 0.49 g (96%). At 125 °C the complete
conversion required ꢃ20 min.
[15] D. Singleton, Tetrahedron Lett. (1973) 1245.
[16] (a) J.G. Leipoldt, L.D.C. Bock, S. S Basson, J.S. van Vollenhoven,
T.I.A. Geber, Inorg. Chim. Acta 25 (1977) L63;
(
(
b) L.J. Botha, S.S. Basson, J.G. Leipoldt, Inorg. Chim. Acta 126
1987) 25.
3
.3.5. Carbonylation of [Rh(CO) Cl ]
2 3 2
[
Rh(CO) Cl ] (0.6 g, 2.26 mmol Rh) was dissolved in
2 3 2
[17] (a) L.A. Oro, M. Esteban, R.M. Claramunt, J. Elguero, C. Foces-
Foces, F.H. Cano, J. Organomet. Chem. 276 (1984) 79;
DMF (15 ml). IR spectrum of the solution contained three
carbonyl stretching bands with maxima related to Rh(III)
monocarbonyl complex (2094 cm ) and to Rh(I) dicarbonyl
(
b) F.L. Barcel o´ , J.C. Besteiro, P. Lahuerta, C. Foces-Foces,
F.H. Cano, M. Martinez-Ripoll, J. Organomet. Chem. 270 (1984)
43.
ꢀ
1
3
ꢀ1
complex (2065 and 1985 cm ). The concentration of
[
18] W.A. Herrman, J.A. Kulpe, W. Konkol, H. Bahrmann, J. Organo-
ꢀ
[
Rh(CO) Cl ] anion (0.075 mmol/ml) calculated from the
2
2
met. Chem. 399 (1990) 85.
ꢀ
1
1
985 cm band intensity corresponded to ꢃ50% of the taken
[19] W.C. Sheldric, B. G u¨ nther, J. Organomet. Chem. 402 (1991)
65.
20] (a) A.M. Trzeciak, E. Wolszczak, J.J. Zi o´ łkowski, New J. Chem. 20
2
amount of [Rh(CO) Cl ] . Evolution of CO was detected by
2
3 2
2
[
IR in the gas taken from the reaction vessel. Farther conver-
sion of Rh(III) monocarbonyl complex into [Rh(CO) Cl ]
(
(
1996) 365;
ꢀ
2
2
b) E. Kwaskowska-Ch e˛ c´ , J.J. Zi o´ łkowski, Transition Met. 8 (1983)
at 125 °C was monitored by IR at 10 min intervals. In
0 min the conversion reached its maximal value, 80%.
1
05.
[21] L.D. Sadekov, A.I. Uraev, A.D. Garnovskii, Uspekhi Khim. 68
1999) 454.
6
(
[
[
22] T.S. Barnard, M.R. Mason, Inorg. Chem. 40 (2001) 5001.
23] A.B. Koudriavtsev, A.T. Teleshev, A.A. Zhdanov, E.E. Nifant’ev,
W. Linert, Monatsh. Chem. 132 (2001) 1001.
Acknowledgements
Financial support from the Russian Foundation for Ba-
sic Research (Project No. 05-03-324630) is gratefully
[
24] F. Ragaini, L. Lunardi, D. Tomasoni, V. Guglielmi, J. Organomet.
Chem. 689 (2004) 3621.