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The oxidation of [Os(P)(CO)(EtOH)] (P = porphyrin dianion) to [Os(P)(O)2] by m-chloroperoxybenzoic acid in CH2Cl2 proceeds through a stable Os(IV) intermediate. The [Os(p-X-TPP)(O)2] (X = Cl, H, OMe, Me) and [Os(TMP)(O)2] complexes have been characterized by UV-vis, 1H NMR, and IR spectroscopy. The crystal structure of [Os(p-Me-TPP)(O)2]·2C4H8O (H2(p-Me-TPP) = meso-tetra-p-tolylporphyrin) has been determined: monoclinic, space group P21/c, a = 11.025 (1) Å, b = 16.977 (2) Å, c = 13.196 (2) Å, β = 110.21 (1)°, Z = 2. The Os-porphinato unit is planar with Os-N = 2.066 (4) Å and Os-O = 1.743 (3) Å. The [Os(P)(O)2] complexes are ineffective in the epoxidation of olefins. Stirring [Os(TPP)(O)2] and [Os(TMP)(O)2] wtih cyclohexene at 52°C yielded cyclohexenol.
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Che et al. (1988) studied this question.
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