The reductive carbonylation of silica-supported MCl3·3H2O (M=Rh, Ir) was studied at atmospheric pressure under CO and under a mixture of CO and H2O. It was observed that these salts may be converted respectively into [Ir(CO)3 Cl]n and [Rh(CO)2Cl]2 under CO. At 70 °C, in the presence of CO and H2O, Ir4(CO)12 is selectively obtained. Under the same experimental conditions [Rh(CO)2Cl]2 sublimes, while at 25 °C the liberated HCl inhibits further reduction to rhodium carbonyl clusters. However, Rh6(CO)16 might easily be obtained, working at 25 °C with CO and H2O, using [Rh(CO)2Cl]2 as the starting material instead of RhCl3. The inhibiting effect on the nucleation process of HCl and the role of water are discussed in the comparison with the reductive carbonylation of a chlorine-free rhodium salt, [Rh(O2CCH3)2]2.

Surface organometallic chemistry: Reductive carbonylation of silica-supported MCl3·3H2O (M=Rh, Ir) / R. Psaro, D. Roberto, R. Ugo, C. Dossi, A. Fusi. - In: JOURNAL OF MOLECULAR CATALYSIS. - ISSN 0304-5102. - 74:1-3(1992), pp. 391-400.

Surface organometallic chemistry: Reductive carbonylation of silica-supported MCl3·3H2O (M=Rh, Ir)

R. Psaro;D. Roberto;R. Ugo;A. Fusi
1992

Abstract

The reductive carbonylation of silica-supported MCl3·3H2O (M=Rh, Ir) was studied at atmospheric pressure under CO and under a mixture of CO and H2O. It was observed that these salts may be converted respectively into [Ir(CO)3 Cl]n and [Rh(CO)2Cl]2 under CO. At 70 °C, in the presence of CO and H2O, Ir4(CO)12 is selectively obtained. Under the same experimental conditions [Rh(CO)2Cl]2 sublimes, while at 25 °C the liberated HCl inhibits further reduction to rhodium carbonyl clusters. However, Rh6(CO)16 might easily be obtained, working at 25 °C with CO and H2O, using [Rh(CO)2Cl]2 as the starting material instead of RhCl3. The inhibiting effect on the nucleation process of HCl and the role of water are discussed in the comparison with the reductive carbonylation of a chlorine-free rhodium salt, [Rh(O2CCH3)2]2.
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/210899
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