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 [Ru^VI(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 (H2dpp) (yield = 75%) based on the Suzuki cross-coupling reaction between phenylboronic acid PhB(OH)2and [2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrin] has been developed. X-Ray diffraction studies of [MII(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 Å from the least-squares plane compared to 0.78 Å for free H2dpp, whereas the Ru and Os atoms are displaced by 0.1006 and 0.0792 Å from the 25-atom porphyrin core respectively. The complex [RuVI(dpp)O2] 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-β-methylstyrene afforded significant amounts of trans-epoxide suggesting that a carboradical mechanism is operative. The crystal structure of the complex [RuIV(dpp)(pz)2] (5), the product of the stoichiometric alkene oxidations, was determined. Magnetic susceptibility measurement (μeff= 3.24 μB) suggests the formulation of RuIVwith two unpaired electrons in its electronic ground state. The Ru-N (pz) bond distances are 2.022(13) and 2.083(12) Å. The reactions of 2 with alkenes in CH2Cl2(with 2% Hpz) follow second-order kinetics: rate = k1[2][alkene]. For norbornene and styrene, the second-order rate constants, k1, in CH2Cl2at 25.9°C are (3.79 ± 0.04) × 10-3and (4.78 ± 0.09) × 10-3dm3mol-1s-1respectively.