15226-74-1Relevant articles and documents
Cleavage of acylcobalt carbonyl with hydridocobalt tetracarbonyl
Azran, Jacques,Orchin, Milton
, p. 197 - 199 (1984)
The reaction CH3(CH2)4COCo(CO)4 + HCo(CO)4 → CH3(CH2)4CHO + Co2(CO)8 proceeds with second-order kinetics (first order in each reactant), k2
THE PREPARATION OF ACYLTETRACARBONYLCOBALT COMPOUNDS FROM KETENES AND HYDRIDOTETRACARBONYLCOBALT
Ungvary, Ferenc
, p. 251 - 256 (1986)
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.
THE REACTION OF TRIPHENYLCARBINOL WITH HCo(CO)4
Matsui, Yasushi,Orchin, Milton
, p. 381 - 384 (1982)
The reaction of Ph3COH with 2 mol of HCo(CO)4 gives Ph3CH in quantitative yield.The reaction is cleanly second order (k2 = 2.50 x 10-4 l mol-1 s-1, in CH2Cl2 at 20 deg C), first order with respect to each reactant.The rate increases markedly with increase in solvent polarity, suggesting Ph3C+ as an intermediate.The rate of the reaction of HCo(CO)4 with Ph3CBF4 is more than 103 as fast as with Ph3COH.No evidence for the functioning of HCo(CO)4 as a hydride donor could be secured.
Electrochemical synthesis and structure of Sn[Co(CO)4]4 and its use as a stable precursor of [Co(CO)4]- for the catalysis of hydrolysis of propylene carbonate
Cabrera, Armando,Samain, Henri,Mortreux, André,Petit, Francis,Welch, Alan J.
, p. 959 - 964 (2008/10/08)
The complex Sn[Co(CO)4]4 (I) has been prepared in high yield by the controlled potential electrolysis of Co2(CO)8 in the presence of a tin anode. The major advantage afforded by this electrochemical synthesis is to produce I quickly and cleanly. Results of an X-ray diffraction study on I are reported. We have established that I and Co2(CO)8 are very active catalysts for the hydrolysis of cyclic organic carbonates. The 100% selectivity in mpnoglycol is in marked contrast to other catalytic systems that require an excess of water to inhibit production of polyglycols. Studies, under various CO pressures, of the catalytic activities of Co2(CO)8 and I during the hydrolysis of propylene carbonate have led us to suggest that (i) [Co(CO)4]- is the active moiety, (ii) I can eliminate Co2(CO)8, and (iii) I is more stable than Co2(CO)8 at low CO pressures. Isotopic analysis of the remaining substrate and products after the hydrolysis of propylene carbonate by H218O show that (iv) the attack of water occurs at the carbonyl site of the carbonate and (v) it is likely that hydration is activated by [Co(CO)4]-.
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.
