Heterolytic Alkyl Hydroperoxide O-O Bond Cleavage by Copper(I) Complexes

被引：22
|
作者：
Tano, Tetsuro [1 ]
Sugimoto, Hideki [1 ]
Fujieda, Nobutaka [1 ]
Itoh, Shinobu [1 ]
机构：
[1] Osaka Univ, Grad Sch Engn, Dept Mat & Life Sci, Div Adv Sci & Biotechnol, Suita, Osaka 5650871, Japan
来源：
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2012年 / 26期
关键词：
Copper; Peroxides; O-O activation; Heterolytic bond cleavage; Alkyl peroxide complexes; III-OOR COMPLEXES; RAY-ABSORPTION SPECTROSCOPY; SPIN FERRIC HYDROPEROXO; NONHEME IRON; SUPEROXIDE REDUCTASE; ELECTRONIC-STRUCTURE; ALKYLPEROXOIRON(III) INTERMEDIATE; REACTIVITY; OXIDATION; LIGANDS;
D O I：
10.1002/ejic.201200555
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reaction of copper(I) complexes and cumene hydroperoxides was examined to demonstrate that heterolytic OO bond cleavage of the peroxides proceeds predominantly to give the corresponding alcohols (cumyl alcohols) as the major product, when the stoichiometry of CuI/peroxide is 2:1. The result is in sharp contrast to the 1:1 reaction between the copper(II) complexes and cumene hydroperoxide, which provides the ketone (acetophenone) as the major product through homolytic OO bond cleavage.
引用
收藏
页码：4099 / 4103
页数：5
相关论文
共 50 条
  • [41] On the energetics of homolytic and heterolytic O-H bond cleavage in flavonoids
    Vaganek, Adam
    Rimarcik, Jan
    Lukes, Vladimir
    Klein, Erik
    COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2012, 991 : 192 - 200
  • [42] HETEROLYTIC C,O-BOND CLEAVAGE OF 4'-NUCLEOTIDE RADICALS
    GIESE, B
    ERDMANN, P
    GIRAUD, L
    GOBEL, T
    PETRETTA, M
    SCHAFER, T
    VONRAUMER, M
    TETRAHEDRON LETTERS, 1994, 35 (17) : 2683 - 2686
  • [43] Metal-bridging mechanism for O-O bond cleavage in cytochrome c oxidase
    Blomberg, MRA
    Siegbahn, PEM
    Wikström, M
    INORGANIC CHEMISTRY, 2003, 42 (17) : 5231 - 5243
  • [44] Reductive cleavage of the O-O bond in multicopper oxidases: a QM/MM and QM study
    Srnec, Martin
    Ryde, Ulf
    Rulisek, Lubomir
    FARADAY DISCUSSIONS, 2011, 148 : 41 - 53
  • [45] Synthetic heme-O2-copper assemblies and reductive O-O cleavage chemistry
    Karlin, Kenneth
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2017, 254
  • [46] Modeling cytochrome oxidase:: A quantum chemical study of the O-O bond cleavage mechanism
    Blomberg, MRA
    Siegbahn, PEM
    Babcock, GT
    Wikström, M
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (51) : 12848 - 12858
  • [47] The nature of the O-O bond in hydroperoxides
    Lysenko, KA
    Antipin, MY
    Khrustalev, VN
    RUSSIAN CHEMICAL BULLETIN, 2001, 50 (09) : 1539 - 1549
  • [48] Alkyl peroxides: Effect of substituent groups on the torsional mode around the O-O bond
    Maciel, Glauciete S.
    Bitencourt, Carla P.
    Ragni, Mirco
    Aquilanti, Vincenzo
    INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 2007, 107 (14) : 2697 - 2707
  • [49] Spectroscopic properties and electronic structure of low-spin FE(III)-alkylperoxo complexes: Homolytic cleavage of the O-O bond
    Lehnert, N., 1600, American Chemical Society (123):
  • [50] Spectroscopic properties and electronic structure of low-spin Fe(III)-alkylperoxo complexes: Homolytic cleavage of the O-O bond
    Lehnert, N
    Ho, RYN
    Que, L
    Solomon, EI
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (34) : 8271 - 8290
12345