15226-74-1Relevant academic research and scientific papers
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
Synthesis of tetranuclear mixed-metal clusters via the reaction of [Co(CO)4]- with closed metal carbonyl trimers. Crystal and molecular structure of [(Ph3P)2N][CoRu3(CO)13]
Steinhardt, Paul C.,Gladfelter, Wayne L.,Harley, A. Dale,Fox, Joseph R.,Geoffroy, Gregory L.
, p. 332 - 339 (1980)
The new clusters HCoRu3(CO)13, HCoRu2Os(CO)13, HCoRuOs2(CO)13, and HCoOs3(CO)13 have been synthesized by allowing K[Co(CO)4] to react with Ru3(CO)12, Ru2Os(CO)12, RuOs2(CO)12, and Os3(CO)12, respectively, followed by protonation. Reaction of K[Co(CO)4] with Fe3(CO)12, Fe2Ru(CO)12, and FeRu2(CO)12 followed by acidification did not lead to the desired hydrido mixed-metal clusters but instead to various other products. Reaction of [PPN][Co(CO)4] (PPN = (Ph3P)2N) with Fe3(CO)12 and Ru3(CO)12 without subsequent acidification gave the salts [PPN][CoFe3(CO)13] and [PPN][CoRu3(CO)13]. The latter was structurally characterized by single-crystal X-ray diffraction. It crystallizes in the space group P1 with Z = 2 and unit cell dimensions a = 9.783 (5) ?, b = 14.768 (5) ?, c = 18.675 (5) ?, α = 110.39 (3)°, β = 99.02 (4)°, γ = 91.44 (4)°, and V = 2489 (4) ?3. Diffraction data (0° w = 0.044 for 6150 independent reflections with I ≥ 3.0σ(I). The molecule contains a tetrahedral CoRu3 core with each Ru atom bonded to three terminal carbonyls, the Co atom bonded to one terminal carbonyl, and a carbonyl ligand bridging each of the three Co-Ru bonds. Analogous reactions of [PPN] [Co(CO)4] with Fe2Ru(CO)12 and FeRu2(CO)12 gave products formulated as [PPN][CoFe2Ru(CO)13] and [PPN][CoFeRu2(CO)13], but these salts were not obtained pure.
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.
REACTION OF METHOXY KETALS AND DIMETHYL CARBONATE WITH SYNTHESIS GAS.
Wegman,Letts
, p. 357 - 369 (1985)
The reaction of dimethoxy ketals and dimethyl carbonate with synthesis gas results in the formation of acetaldehyde. In the case of methoxy ketals, the reaction is carried out with a cobalt catalyst at 130 degree C and 2500 psi. Th rate of acetaldehyde formation is 4. 0 M h** minus **1. The reaction of dimethyl carbonate requires a cobalt-iodide catalyst and operating conditions of 180 degree C and 4000 psi. In this case, the rate of formation of acetaldehyde approaches 30 M h** minus **1. Mechanisms are discussed which are consistent with results obtained from high pressure infrared studies and stoichiometric model reactions.
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.
Octacarbonyl dicobalt-catalyzed selective transformation of ethyl diazoacetate into organic products containing the ethoxycarbonyl carbene building block
Tuba, Robert,Ungváry, Ferenc
, p. 59 - 67 (2008/10/08)
In the presence of 1 mol% octacarbonyl dicobalt ethyl diazoacetate can be transformed at room temperature and carbon monoxide pressure selectively into diethyl 2-diazo-3-oxo-pentanedicarboxylate or in the presence of an alcohol (methanol, ethanol, tert-bu
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]-.
Alkylcobalt carbonyls. 9. Alkoxy-, silyloxy-, and hydroxy-substituted methyl- and acetylcobalt carbonyls. Reduction of formaldehyde to methanol by hydridocobalt tetracarbonyl
Sisak, Attila,Sámpár-Szerencsés, Ella,Galamb, Vilmos,Németh, László,Ungváry, Ferenc,Pályi, Gyula
, p. 1096 - 1100 (2008/10/08)
(Alkoxymethyl)-, ((silyloxy)methyl)-, and (hydroxymethyl)cobalt and (alkoxyacetyl)-, ((silyloxy)acetyl)-, and (hydroxyacetyl)cobalt tetracarbonyls and phosphine-substituted derivatives were prepared. The interconversions of these compounds by carbonylatio
Steric and Electronic Factors That Control Two-Electron Processes between Metal Carbonyl Cations and Anions
Zhen, Yueqian,Feighery, William G.,Lai, Chung-Kung,Atwood, Jim D.
, p. 7832 - 7837 (2007/10/02)
Reactions of metal carbonyl cations (Mn(CO)6(+), Re(CO)6(+), Mn(CO)5PPh3(+), Mn(CO)4(PPh3)2(+), Mn(CO)5PEt3(+), Mn(CO)5PPh2Me(+), Re(CO)5PPh3(+), and CpFe(CO)3(+)) with metal carbonyl anions (Co(CO)3PPh3(-), Co(CO)4(-), Mn(CO)5(-), Mn(CO)4PPh3(-), Mn(CO)4PEt3(-), Mn(CO)4PPh2Me(-), Mn(CO)3(PPh3)2(-), CpFe(CO)2(-), Re(CO)5(-), and Re(CO)4PPh3(-)) are reported.Peak potentials are reported for all ions, and nucleophilicites (as measured by reaction with MeI) are reported for the anions.Reaction of any metal carbonyl cation with any metal carbonyl anion leads ultimately to binuclear products, which are the thermodynamic products.The binuclear products are formed by single-electron transfer.In over half of the reactions between metal carbonyl cations and anions, a two-electron change results in a new metal carbonyl cation and anion.The two-electron change may be considered mechanistically as a CO(2+) transfer with the more nucleophilic of the two anions retaining the CO(2+).The kinetic and thermodynamic driving forces and the suggested mechanism are examined.
Photochemical Splitting of a Polar Metal-Metal Bond by Metal to Metal Charge Transfer Excitation of
Vogler, Arnd,Kunkely, Horst
, p. 132 - 134 (2007/10/02)
The polar metal-metal bond of I-Co-I(CO)4> was cleaved photochemically by metal to metall (Co-IAu+I) charge transfer excitation.Metallic gold, Ph3P and were formed as products. - Keywords: Photolysis, Metal-Metal Bond, Charge Transfer Excitation
