Heinz W. Sternberg

Solubilization of an lvb coal by reductive alkylation

Abstract Pocahontas (lvb) coal, when treated with alkali metal in tetrahydrofuran in the presence of a small amount of naphthalene, is converted to a ‘coal anion’. The coal anion is formed by transfer of negative charges from the alkali metal to the aromatic clusters in coal with naphthalene acting as an electron transfer agent. The coal anion, containing 12 charges per 100 carbon atoms, is readily alkylated by alkyl halides. The alkylated coals contain 8 alkyl groups per 100 carbon atoms and are soluble in benzene at room temperature. Five of the alkyl groups are attached to carbon atoms and the remaining three to oxygen atoms. The molecular weight of the alkylated coals is in the same range (3000–4000) as that of petroleum asphaltenes. The solubility in benzene of alkylated coal and of petroleum asphaltenes is believed to be due to the presence of alkyl groups which prevent stacking of the aromatic clusters.

61 Homogeneous Metal Carbonyl Reactions and Their Relation to Heterogeneous Catalysis

Publisher Summary This chapter discusses homogeneous metal carbonyl reactions and their relation to heterogeneous catalysis. Catalytic reactions generally involve the chemical reaction of atoms or molecules with a surface, and various types of surface complexes have been postulated as intermediates. A study of metal carbonyls and their reactions offers a unique and profitable way for obtaining information concerning the nature of these complexes. Metal carbonyls may be considered as parts of the surface of a transition metal, which are cut off from the surface and stabilized by carbon monoxide molecules. The chapter presents a study where cyclohexene was chosen because it yields only one aldehyde, which is hexahydrobenzaldehyde. The rate of hydroformylation was found to be first order with respect to the olefin and approximately proportional to the amount of cobalt present.