The kinetics of the oxidation of glutathione by diaquatetrakis(2,2'-bipyridine)-#-oxo diruthenium(III) ion in aqueous HC104 have been investigated. The reaction obeys the empirical rate law: -2d [oxidant-]/dt = k[oxidant] [reductant]/[H § ] where k=7.42_+0.40• -1 at 25.5~ [H+]= 0.005-0.05 M and I = 1.0 M (LiC104). Free radicals are important in the reaction and a mechanism consistent with the experimental results has been postulated.
New cationic trialkylphosphines [P(CH2NH2R){CH2N(R)CH2N(R)CH2}]+ (R = C6H5CH2, a; 4-FC6H4CH2, b), as their Cl− (1a, 1b), SbF6
− (2a, 2b), and PF6
− (3a, 3b) salts, are described. The phosphine framework is conformationally locked, in the solid state, through pairs of intramolecular N−H···N hydrogen bonds which are maintained in the RuII and RhIII complexes 4 and 5. Phosphines 1a−3b can be considered as charged variants of the well-known PTA ligand.
Rare examples of homodinuclear zwitterionic Pd II and Pt II complexes with bridging, two-coordinate P{cyclo-CH 2 N(R)CHN-(R)CH 2 } ligands (R = 4-FC 6 H 4 CH 2 , C 6 H 5 CH 2 ) have been characterized by single-crystal X-ray diffraction using synchrotron radiation. Short N-C distances and enlarged N-C-N bond angles support electron delocalization in the central N-C-N backbone.
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