Saddle-shaped dioxo-ruthenium(VI) and -osmium(VI) 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphyrin (H2dpp) complexes.: Synthesis, spectral characterisation and alkene oxidation by [RuVI(dpp)O2]

An improved procedure for the preparation of the saddle-distorted porphyrin 2,3,5,7,8,10,12,13,15, 17,18,20-dodecaphenylporphyrin (H(2)dpp) (yield = 75%) based on the Suzuki cross-coupling reaction between phenylboronic acid PhB(OH)(2) and [2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin] has been developed. X-Ray diffraction studies of[M-II(dpp)(CO)(py)] (M = Ru 1 or Os 3) showed that 1 and 3 are isostructural, and the porphyrin macrocycles exhibit severe out-of-plane saddle and ruffle distortions. In both 1 and 3 the pyrrole rings are alternately tilted up and down with respect to the least-squares plane of the 25-atom porphyrin core, and the pyrrole carbons experience an average displacement of 0.769 Angstrom from the least-squares plane compared to 0.78 Angstrom for free H(2)dpp, whereas the Ru and Os atoms are displaced by 0.1006 and 0.0792 Angstrom from the 25-atom porphyrin core respectively. The complex [Ru-VI(dpp)O-2] 2, prepared by m-chloroperoxybenzoic acid oxidation, is an active oxidant for alkene epoxidations. In CH2Cl2 [containing 2%(w/w) pyrazole], styrene, norbornene and cis-stilbene were oxidised selectively to their respective epoxides in excellent yield. Complete stereoretention was observed for the oxidation of cis-stilbene, however oxidation of cis-beta-methylstyrene afforded significant amounts of trans-epoxide suggesting that a carboradical mechanism is operative. The crystal structure of the complex [Ru-IV(dpp)(pz)(2)] (5), the product of the stoichiometric alkene oxidations, was determined. Magnetic susceptibility measurement (mu(eff) = 3.24 mu(B)) suggests the formulation of Ru-IV with two unpaired electrons in its electronic ground state. The Ru-N (pz) bond distances are 2.022(13) and 2.083(12) Angstrom. The reactions of 2 with alkenes in CH2Cl2 (with 2% Hpz) follow second-order kinetics: rate = k(1)[2][alkene]. For norbornene and styrene, the second-order rate constants, k(1), in CH2Cl2 at 25.9 degrees C are (3.79 +/- 0.04) x 10(-3) and (4.78 +/- 0.09) x 10(-3) dm(-3) mol(-1) s(-1) respectively.