82182-04-5Relevant academic research and scientific papers
CIDNP EVIDENCE FOR RADICAL INTERMEDIATES IN THE HYDROFORMYLATION AND REDUCTION OF STYRENE BY HCo(CO)4/CO
Bockman, Michael T.,Garst, John F.,King, R. Bruce,Marko, Laszlo,Ungvary, Ferenc
, p. 165 - 170 (1985)
Reactions of styrene with HCo(CO)4 in CH2Cl2, CD2Cl2 and C6D6 give ethylbenzene, 2-phenylpropanal, and probably 2-phenylpropanoylcobalt tetracarbonyl with nuclear spin polarization consistent with formation through initially singlet radical pairs .CHr.Co(CO)4>.This is the first report of CIDNP in a hydroformylation product.
Reactions of homo- and heterobinuclear cobalt carbonyls with metal carbonyl hydrides
Kovács, István,Sisak, Attila,Ungváry, Ferenc,Markó, László
, p. 1873 - 1877 (2008/10/08)
HMn(CO)5, HMo(CO)3Cp, and HFe(CO)2Cp (Cp = cyclopentadienyl) were found to react with Co2(CO)8 forming HCo(CO)4 and the corresponding mixed-metal carbonyl dimers. It was shown that HMo(CO)3Cp transferred the hydrogen atom to Co2(CO)8 and CoMn(CO)9 in reversible processes. The substituted hydride HMn(CO)4P-n-Bu3 and Co2(CO)8 afforded (CO)4CoMn(CO)4P-n-Bu3 which was characterized by elementary analysis and IR and mass spectroscopy. Its reaction with HMo(CO)3Cp gave HMn(CO)4P-n-Bu3 and CoMo(CO)7Cp. The attack of the hydrides took place in mixed-metal complexes exclusively on the cobalt atom. A mechanism in which the hydrides oxidatively add to a coordinatively unsaturated Co center formed by CO loss is proposed.
THE PREPARATION OF ACYLTETRACARBONYLCOBALT COMPOUNDS FROM KETENES AND HYDRIDOTETRACARBONYLCOBALT
Ungvary, Ferenc
, p. 251 - 256 (2007/10/02)
Ketenes (R1R2C=C=O, R1, R2= H or alkyl)react rapidly at -79 deg C with hydridotetracarbonylcobalt in a 1/1 molar ratio to form quantitatively the corresponding acyltetracarbonylcobalts, which can be isolated in good to exellent yields.Electron-withdrawing substituents in the ketene lower the reactivity towards HCo(CO)4.
Reaction of HCo(CO)4 and CO with styrene. Mechanism of (α-Phenylpropionyl)- and (β-Phenylpropionyl)cobalt tetracarbonyl formation
Ungváry, Ferenc,Markó, László
, p. 1120 - 1125 (2008/10/08)
Cobalt tetracarbonyl hydride and styrene react in the presence of carbon monoxide to form ethylbenzene and (α-phenylpropionyl)cobalt tetracarbonyl; both reactions are first order in HCo(CO)4 and PhCH=CH2 and independent of CO and Co2(CO)8 concentration. The kinetic data suggest a common radical pair intermediate for both reactions. (α-Phenylpropionyl)cobalt tetracarbonyl is not the final product of the reaction: it slowly decomposes into ethylbenzene, CO, and Co2(CO)8 and partly isomerizes into (β-phenylpropionyl) cobalt tetracarbonyl. Accordingly, among these acyl complexes the branched-chain isomer is the kineticly controlled product and the straight-chain isomer the thermodynamicly controlled product.
