Catalytic Hydrogenation by Pentacyanocobaltate(II)

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

“…A number of groups subsequently studied this system and found that [(CN) 5 CoH] 3– was formed under the reaction conditions . In 1962, Kwiatek and co-workers reported that [(CN) 5 Co III H] 3– was able to catalytically reduce a wide array of conjugated functional groups such as aliphatic dienes, conjugated aromatic olefins, α,β-unsaturated carbonyls (acids, esters, and aldehydes), 1,2-diketones, epoxides, and azoxy compounds under an atmosphere of hydrogen gas (1 atm). , These substrates include styrene, isoprene, 1,3-cyclohexadiene, tiglic aldehyde, methacrylic acid, sorbic acid, cinnamic acid, methyl methacrylate, benzil, cyclohexene oxide, styrene oxide, and azoxybenzene, among others. Each was reduced by one degree of unsaturation.…”

Sigma‐Pi Rearrangements of Organotransition Metal Compounds

“…Ally1 chloride reacts with a methanolic solution of carbonylchlororhodium in the presence of a little water to give a compound with the structure (25). On addition of thallium cyclopentadienide the complex (26) is obtained, the NMR spectra of which indicates that one allyl group is n-bonded and one is a-bonded 1461.…”

“…Powell Cyclopentadienide ion would be expected to exhibit a similar effect to carbonyl and especially to cyanide ion in ability to cause a x-a rearrangement [451. Ally1 chloride reacts with a methanolic solution of carbonylchlororhodium in the presence of a little water to give a compound with the structure (25). On addition of thallium cyclopentadienide the complex (26) is obtained, the NMR spectra of which indicates that one allyl group is n-bonded and one is a-bonded 1461. action between allyl iodide and pentacarbonyliron gives a compound with an empirical formula C3H5Fe(C0)31.…”

Homogeneous hydrogenations ofα, β-unsaturated compounds using pentacyanocobaltate (II) anion as catalyst system

“…Owing to the facility with wb_ich the pentacyanocobaltate (II), K3Co(CN)5, species reacts with hydrogen to f o r m a hydrido complex, tlª system has been used in the catalytic homogeneous hydrogenation of various org~nic substrates (Kwiatek et al 1963;Kwiatek 1967;Kwiatek 1968;Jackmann 1968). This catalyst hydrogen~tes a wide range of organic compounds with a fair amount of selectivity.…”