PMID- 15877428
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20050615
LR  - 20050509
IS  - 0020-1669 (Print)
IS  - 0020-1669 (Linking)
VI  - 44
IP  - 10
DP  - 2005 May 16
TI  - Aerobic catechol oxidation catalyzed by a bis(mu-oxo)dimanganese(III,III) complex 
      via a manganese(II)-semiquinonate complex.
PG  - 3473-8
AB  - A 3,5-di-tert-butyl-1,2-semiquinonato (DTBSQ) adduct of Mn(II) was prepared by a 
      reaction between Mn(II)(TPA)Cl(2) (TPA = tris(pyridin-2-ylmethyl)amine) and DTBSQ 
      anion and was isolated as a tetraphenylborate salt. The X-ray crystal structure 
      revealed that the complex is formulated as a manganese(II)-semiquinonate complex 
      [Mn(II)(TPA)(DTBSQ)](+) (1). The electronic spectra in solution also indicated 
      the semiquinonate coordination to Mn. The exposure of 1 in acetonitrile to 
      dioxygen afforded 3,5-di-tert-butyl-1,2-benzoquione and a 
      bis(mu-oxo)dimanganese(III,III) complex [Mn(III)(2)(mu-oxo)(2)(TPA)(2)](2+) (2). 
      The reaction of 2 with 3,5-di-tert-butylcatechol (DTBCH(2)) quantitatively 
      afforded two equivalents of 1 under anaerobic conditions. The highly efficient 
      catalytic oxidation of DTBCH(2) with dioxygen was achieved by combining the above 
      two reactions, that is, by constructing a catalytic cycle involving both 
      manganese complexes 1 and 2. It was revealed that dioxygen is reduced to water 
      but not to hydrogen peroxide in the catalytic cycle.
FAU - Hitomi, Yutaka
AU  - Hitomi Y
AD  - Department of Molecular Engineering, Graduate School of Engineering, Kyoto 
      University, Katsura, Nishikyo-ku, Japan. hitomi@moleng@.kyoto-u.ac.jp
FAU - Ando, Akira
AU  - Ando A
FAU - Matsui, Hajime
AU  - Matsui H
FAU - Ito, Tomoyuki
AU  - Ito T
FAU - Tanaka, Tsunehiro
AU  - Tanaka T
FAU - Ogo, Seiji
AU  - Ogo S
FAU - Funabiki, Takuzo
AU  - Funabiki T
LA  - eng
PT  - Journal Article
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
EDAT- 2005/05/10 09:00
MHDA- 2005/05/10 09:01
CRDT- 2005/05/10 09:00
PHST- 2005/05/10 09:00 [pubmed]
PHST- 2005/05/10 09:01 [medline]
PHST- 2005/05/10 09:00 [entrez]
AID - 10.1021/ic050109d [doi]
PST - ppublish
SO  - Inorg Chem. 2005 May 16;44(10):3473-8. doi: 10.1021/ic050109d.