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Extra info for Large Molecules
A silver I salt of TPP containing two silver atoms has been described; it produces an electronic spectrum like that of the porphyrin dianions [Rothemund (153)]. Ag~I phthalocyanine is photolabile [Lever (122)]. Ag II. This is the usual oxidation state of silver in the porphyrin cavity and is obtained from silverI salts and the free porphyrin bases. 03) [Kneubi~hl (114)]. AgIII. The chemical oxidation of AgII OEP leads to Ag III OEP salts, which are stable, diamagnetic and produce a normal electronic spectrum [522 (25,200) 516 (9,800) 404 (131,000)] [Kadish (109)].
Addition of olefins to a solution of CoII Meso results in an immediate shift of the CoII 393-nm Soret band to the CoIII 411-nm absorption. -H. Fuhrhop Various hydrocarbons have been used in this reaction, but no product analysis has been performed on any of them [Tsutsui (180), (182)]. These experimental results indicate effcient activation of molecular oxygen, and the intermediacy of superoxide and/or peroxo complexes of the cobalt porphyrins is probable. ColITpP reacts with tetracyanoethylene (TCNE) to a 1:1 complex, where nitrogens of the nitrile groups interact with the cobalt (Eqn.
48 G) but not through the nitrogens [Felton (59)]. The relatively large linewidth can be explained by the degeneracy of the outer orbitals which yields some orbital moment contributions (see III), but surprisingly the chlorin esr spectra yield similar broad lines [Fuhrhop (70a)]. This phenomenon has still to be evaluated. At low temperatures (--70 °C) a dimer with an absorption band at 950 nm has been observed which did not produce an esr spectrum [Felton (59)]. 27 V) [Diehn (47), Fuhrhop (78).