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Volumn , Issue 7, 2001, Pages 1235-1247

Alcohol oxidation by dioxygen and aldehydes catalysed by square-planar cobalt(III) complexes of disubstituted oxamides and related ligands

Author keywords

Alcohols; Amides; Catalysis; Cobalt; Oxidations; X ray absorption spectroscopy

Indexed keywords

ALCOHOL; ALDEHYDE; AMIDE; BENZENE DERIVATIVE; COBALT; HYDROGEN; LIGAND; OXAMIC ACID; OXYGEN; PHENETHYL ALCOHOL;

EID: 0035066480     PISSN: 1434193X     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0690(200104)2001:7<1235::aid-ejoc1235>3.3.co;2-w     Document Type: Article
Times cited : (71)

References (103)
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    • note
    • 2O.
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    • The near K-edge structures originate from electronic transitions from the occupied 1s core orbital of the metal ion to the excited vacant metal orbitals of proper symmetry, according to the selection rule Δl = ± 1. In a simplified one-electron approximation, these are 1s (l = 0) → 4p (l = 1) allowed transitions (edge structures) and 1s (/ = 0) → 3d (l = 2) forbidden transitions (pre-edge structures). The XANES spectra are therefore closely related to the electronic and stereochemical properties of the metal complexes (e.g., metal oxidation state, coordination geometry and ligand environment).
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    • note
    • II,III-edges, which are more sensitive than the K-edge to the occupancy of the 3d orbitals, are planned in order to address this problem.
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    • 2opba)], formally a square-planar cobalt(IV) complex.
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    • note
    • The limited solubility of the cobalt catalysts in acetonitrile precluded a rigorous examination of the kinetics of the catalytic system. However, the oxidation rate of 1-phenylethanol could be evaluated qualitatively under a standard set of reaction conditions by measuring the yield of acetophenone at regular intervals.
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    • note
    • More probably, the pivalic acid formed as the by-product from the autoxidation of pivalaldehyde was then immediately neutralised by the added base, thus preventing a high concentration of pivalic acid from building up and, consequently, precluding decomposition of the cobalt catalyst through protonation and decomplexation of the oxamide ligand from the metal centre. Furthermore, the possible competition between the alcohol substrate and the aldehyde co-oxidant for the oxidation reaction can be avoided, or at least impeded, if the latter is kept low by sequential step addition (see discussion below).
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    • A very recent report of the crystal structure of the activated oxygen intermediate of cytochrome P450cam, an enzyme that hydroxylates camphor, are consistent with an oxo-iron formulation, thus confirming much of what had previously been proposed on the basis of spectroscopic studies of various cytochrome P450 enzymes and model compounds; I. Schlichting, J. Berendzen, K. Chu, A. M. Stock, S. A. Maves, D. E. Benson, R. M. Sweet, D. Ringe, G. A. Petsko, S. G. Sligar, Science 2000, 287, 1615.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.