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DOI: 10.1055/sos-SD-001-00322

Malacria, M.; Aubert, C.; Renaud, J.-L.Science of Synthesis, (20011490.

Tetracarbonylhydridocobalt(I) (64) was one of the first carbonyl hydrides to be discovered and secured its place in chemical history because of its role in the commercially important oxo reaction.[‌225‌] This complex has been described as being able to catalyze the hydrogenation, hydrogenolysis, and also the silylformylation of alkenes.[‌226‌] Complex 64 is readily obtained by a variety of reactions, such as the direct synthesis from carbon monoxide and either cobalt metal and hydrogen under high pressure (25MPa) or cobalt(II) compounds in the presence of moisture or octacarbonyldicobalt(0) with hydrogen under pressure at elevated temperatures;[‌227‌] however, all of these reactions proceed in low yield. The most convenient laboratory synthesis is by the acidification of salts containing the tetracarbonylcobalt anion. The best yields are obtained from the hexapyridinecobalt(II) salt 84, which is prepared from octacarbonyldicobalt(0) (83) and pyridine. Acidification with sulfuric acid gives 64 (Scheme 59).[‌228‌]

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