Fundamental metal carbonyl equilibria.: II. A quantitative study of the equilibrium between dirhodium octacarbonyl and TETRARHODIUM DODECACARBONYL (cas 19584-30-6) under carbon monoxide pressure☆

Add time:08/27/2019    Source:sciencedirect.com

The reversible reaction of Rh4(CO)12 with carbon monoxide under pressure to yield thermally unstable Rh2(CO)8 has been studied by high-pressure infrared spectroscopy. The equilibrium constant and the thermodynamic parameters of this reaction have been determined in the temperature range +30 to −30°C, at 100 to 200 bar CO pressure with n-hexane as solvent: ΔH0 45.5 ± 1.3 kJ mol−1, ΔS0 266.6 ± 4.7 J mol−1 K−1. A detailed comparison with the analogous cobalt carbonyl system is presented. Preliminary kinetic measurements show that the rate of the cluster-breaking reaction for Rh4(CO)12 with CO at −22°C is ca. 500-times faster than that for the corresponding cobalt cluster.

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