631-36-7Relevant articles and documents
Heterogeneous Rates of Electron Transfer. Application of Cyclic Voltammetric Techniques to Irreversible Electrochemical Processes
Klingler, R. J.,Kochi, J. K.
, p. 4790 - 4798 (1980)
The anodic peak potentials in the irreversible cyclic voltammograms of various homoleptic alkylmetals in acetonitrile show a striking linear correlation with their ionization potentials ID determined in the gas phase.Application of various transient electrochemical techniques proves that the electrode process arises from a totally irreversible ECE sequence in which the peak potential is determined solely by the kinetics of heterogeneous electron transfer and diffusion-uncomplicated by any follow-up chemical reaction.As a result, the anodic peak potential Ep can be directly related to the activation free energy for electron transfer, and the correlation of EP and ID represents a linear free-energy relationship.The mechanism of heterogeneous electron transfer is described as an outer-sphere process, dependent only on the driving force for one-electron oxidation and independent of steric effects of the alkylmetal.The close relationship between the activated compexes for heterogeneous and homogeneous electron transfer is emphasized in a direct comparison of the electrochemical process with the oxidation of the same alkylmetals by a series of poly(pyridine)iron(III) complexes in solution.
Towards Naked Zinc(II) in the Condensed Phase: A Highly Lewis Acidic ZnII Dication Stabilized by Weakly Coordinating Carborate Anions
Adet, Nicolas,Specklin, David,Gourlaouen, Christophe,Damiens, Thibault,Jacques, Béatrice,Wehmschulte, Rudolf J.,Dagorne, Samuel
supporting information, p. 2084 - 2088 (2020/11/30)
The employment of the hexyl-substituted anion [HexCB11Cl11]? allowed the synthesis of a ZnII species, Zn[HexCB11Cl11]2, 3, in which the Zn2+ cation is only weakly coordinated to two carborate counterions and that is soluble in low polarity organic solvents such as bromobenzene. DOSY NMR studies show the facile displacement of at least one of the counterions, and this near nakedness of the cation results in high catalytic activity in the hydrosilylation of 1-hexene and 1-methyl-1cyclohexene. Fluoride ion affinity (FIA) calculations reveal a solution Lewis acidity of 3 (FIA=262.1 kJ mol?1) that is higher than that of the landmark Lewis acid B(C6F5)3 (FIA=220.5 kJ mol?1). This high Lewis acidity leads to a high activity in catalytic CO2 and Ph2CO reduction by Et3SiH and hydrogenation of 1,1-diphenylethylene using 1,4-cyclohexadiene as the hydrogen source. Compound 3 was characterized by multinuclear NMR spectroscopy, mass spectrometry, single crystal X-ray diffraction, and DFT studies.
MONONUCLEAR IRON COMPLEX AND ORGANIC SYNTHESIS REACTION USING SAME
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Paragraph 0218-0220, (2016/12/01)
Provided is a mononuclear iron complex that comprises an iron-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. In formula (1), R 1 -R 6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R 1 -R 3 and one of R 4 -R 6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.
