Catalysis of carbon monoxide hydrogenation by soluble mononuclear complexes

Autor:	H. M. Feder, J. W. Rathke
Rok vydání:	1978
Předmět:	Heptane Chemistry Methyl formate Inorganic chemistry Enthalpy chemistry.chemical_element General Chemistry Biochemistry Medicinal chemistry Catalysis chemistry.chemical_compound Colloid and Surface Chemistry Methanol Benzene Cobalt Carbon monoxide
Zdroj:	Journal of the American Chemical Society. 100:3623-3625
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja00479a069
Popis:	The homogeneous hydrogenation of CO to CH/sub 3/OH, higher primary alcohols and their formate esters in the presence of Co/sub 2/(CO)/sub 8/ using benzene, heptane, and p-dioxane as solvents is reported. The principal rate-determining step is first order in the soluble mononuclear species, HCo(CO)/sub 4/, and the catalysis by cobalt atom dusters or precipitated metal is at most a minor path. Based on paired experiments in benzene (200,220/sup 0/C), and inp-dioxane (182,196/sup 0/C), the apparent activities enthalpy for formation of CO hydrogenation products is 40.7 kcal/mol. This result is compatible with a strongly endothermic rate-determining step in which hydrogen atom transfer to CO yields formyl and cobalt tetracarbonyl radical pairs. Pseudo first-order rate constants for the formation of methanol and total product were found to be 1.3 x 10/sup -5/ s/sup -1/ and 1.46 x 10/sup -5/ s/sup -1/, respectively, and proportionately between hydrogenation rate and concentration of HMn(CO)/sub 5/ was observed.
Databáze:	OpenAIRE
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