| Abstract: | beta-Halogenated dioxoruthenium(VI) porphyrin complexes Ru(VI)(F(28)-tpp)O(2)] F(28)-tpp=2,3,7,8,12,13, 17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and Ru(VI)(beta-Br(8)-tmp)O(2)] beta-Br(8)-tmp=2,3,7,8,12,13,17,18-octabromo-5,10,15,20- tetrakis(2,4,6-trimethylphenyl)porphyrinato(2-)] were prepared from reactions of Ru(II)(por)(CO)] por=porphyrinato(2-)] with m-chloroperoxybenzoic acid in CH(2)Cl(2). Reactions of Ru(VI)(por)O(2)] with excess PPh(3) in CH(2)Cl(2) gave Ru(II)(F(20)-tpp)(PPh(3))(2)] F(20)-tpp=5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato(2-)] and Ru(II)(F(28)-tpp)(PPh(3))(2)]. The structures of Ru(II)(por)(CO)(H(2)O)] and Ru(II)(por)(PPh(3))(2)] (por=F(20)-tpp, F(28)-tpp) were determined by X-ray crystallography, revealing the effect of beta-fluorination of the porphyrin ligand on the coordination of axial ligands to ruthenium atom. The X-ray crystal structure of Ru(VI)(F(20)-tpp)O(2)] shows a Ru=O bond length of 1.718(3) A. Electrochemical reduction of Ru(VI)(por)O(2)] (Ru(VI) to Ru(V)) is irreversible or quasi-reversible, with the E(p,c)(Ru(VI/V)) spanning -0.31 to -1.15 V versus Cp(2)Fe(+/0). Kinetic studies were performed for the reactions of various Ru(VI)(por)O(2)], including Ru(VI)(F(28)-tpp)O(2)] and Ru(VI)(beta-Br(8)-tmp)O(2)], with para-substituted styrenes p-X-C(6)H(4)CH=CH(2) (X=H, F, Cl, Me, MeO), cis- and trans-beta-methylstyrene, cyclohexene, norbornene, ethylbenzene, cumene, 9,10-dihydroanthracene, xanthene, and fluorene. The second-order rate constants (k(2)) obtained for the hydrocarbon oxidations by Ru(VI)(F(28)-tpp)O(2)] are up to 28-fold larger than by Ru(VI)(F(20)-tpp)O(2)]. Dual-parameter Hammett correlation implies that the styrene oxidation by Ru(VI)(F(28)-tpp)O(2)] should involve rate-limiting generation of a benzylic radical intermediate, and the spin delocalization effect is more important than the polar effect. The k(2) values for the oxidation of styrene and ethylbenzene by Ru(VI)(por)O(2)] increase with E(p,c)(Ru(VI/V)), and there is a linear correlation between log k(2) and E(p,c)(Ru(VI/V)). The small slope (approximately 2 V(-1)) of the log k(2) versus E(p,c)(Ru(VI/V)) plot suggests that the extent of charge transfer is small in the rate-determining step of the hydrocarbon oxidations. The rate constants correlate well with the C-H bond dissociation energies, in favor of a hydrogen-atom abstraction mechanism. |
