title: Phenylthiyl radical complexes of gallium(III), iron(III), and cobalt(III) and comparison with their phenoxyl analogues.
abstract: Three hexadentate, asymmetric pendent arm macrocycles containing a 1,4,7-triazacyclononane-1,4-diacetate backbone and a third, N-bound phenolate or thiophenolate arm have been synthesized. In [L(1)](3)(-) the third arm is 3,5-di-tert-butyl-2-hydroxybenzyl, in [L(2)](3)(-) it is 2-mercaptobenzyl, and in [L(3)](3)(-) it is 3,5-di-tert-butyl-2-mercaptobenzyl. With trivalent metal ions these ligands form very stable neutral mononuclear complexes [M(III)L(1)] (M = Ga, Fe, Co), [M(III)L(2)] (M = Ga, Fe, Co), and [M(III)L(3)] (M = Ga, Co) where the gallium and cobalt complexes possess an S = 0 and the iron complexes an S = (5)/(2) ground state. Complexes [CoL(1)].CH(3)OH.1.5H(2)O, [CoL(3)].1.17H(2)O, [FeL(1)].H(2)O, and [FeL(2)] have been characterized by X-ray crystallography. Cyclic voltammetry shows that all three [M(III)L(1)] complexes undergo a reversible, ligand-based, one-electron oxidation generating the monocations [M(III)L(1)(*)](+) which contain a coordinated phenoxyl radical as was unambiguously established by their electronic absorption, EPR, and Mössbauer spectra. In contrast, [M(III)L(2)] complexes in CH(3)CN solution undergo an irreversible one-electron oxidation where the putative thiyl radical monocationic intermediates dimerize with S-S bond formation yielding dinuclear disulfide species [M(III)L(2)-L(2)M(III)](2+). [GaL(3)] behaves similarly despite the steric bulk of two tertiary butyl groups at the 3,5-positions of the thiophenolate, but [Co(III)L(3)] in CH(2)Cl(2) at -20 to -61 degrees C displays a reversible one-electron oxidation yielding a relatively stable monocation [Co(III)L(3)(*)](+). Its electronic spectrum displays intense transitions in the visible at 509 nm (epsilon = 2.6 x 10(3) M(-)(1) cm(-)(1)) and 670sh, 784 (1.03 x 10(3)) typical of a phenylthiyl radical. The EPR spectrum of this species at 90 K proves the thiyl radical to be coordinated to a diamagnetic cobalt(III) ion (g(iso) = 2.0226; A(iso)((59)Co) = 10.7 G).
authors: Max-Planck-Institut für Strahlenchemie, D-45470 Mülheim an der Ruhr, Germany.
authors: S
authors: S
authors: Kimura
authors: E
authors: E
authors: Bill
authors: E
authors: E
authors: Bothe
authors: T
authors: T
authors: Weyhermüller
authors: K
authors: K
authors: Wieghardt
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D019281:Dimerization; D005609:Free Radicals; D005708:Gallium / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D013058:Mass Spectrometry; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010636:Phenols / Q000138:chemical synthesis / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D008024:Ligands; D010636:Phenols; D013438:Sulfhydryl Compounds; C042329:phenoxy radical; D003035:Cobalt; D005708:Gallium; D007501:Iron