Cofaciale Bis(metallo)diporphyrine als potentielle molekulare Katalysatoren für Mehrelektronenreduktionen und ‐oxidationen kleiner Moleküle

An in-situ Raman study of the effect of the support for adsorbed iridium-chelates in catalysing oxygen reduction

“…It is, however, remarkable that the selectivity of these chelates in oxygen reduction is so strongly influenced by the support. This observation is also briefly mentioned by Collman et al [16]. One can ask why only the selectivity is influenced, since the same activation-deactivation phenomena are present on both supports.…”

“…Collman and coworkers [2,16] have proposed a dual site mechanism to explain the four-electron reduction of oxygen at IrOEP I Cp. In his view, the active species is the dimer (IrOEP) 2, which reacts with oxygen to form a /x-peroxo species which is then reduced to water and the original dimer, thus closing the catalytic cycle.…”

Metal Complexes of a Biconcave Porphyrin with D4-Structure—Versatile Chiral Shift Agents

“…Recrystallisation from acetone/water gave Zn II porphyrin 3 (65.7 mg). Yield: 96 %; 1 H NMR (300 MHz, CDCl 3 ): d 10.67 (s,4 H;H m ),7.91 (d,J 1.9 Hz,8 H;H 1,5 ),7.81 (d,J 7.8 Hz,8 H;H 4,8 ),7.13 (s,8 H;H 9,10 ),7.04 (dd,J 1.9,7.8 Hz,8 H;H 3,7 ), 1.27 (s, 72 H); 13 Preparation of crystals: In a small glass tube, a stock solution (0.1 mL) of Co II -porphyrinate 7 [2a] (6.2 mg, 4.8 mmol) in 1,2-dichlorobenzene (4 mL) were mixed at room temperature with a solution of [60]-fullerene (0.87 mg, 0.12 mmol) in of benzene (1 mL). The tube was flushed with nitrogen and then closed.…”

“…[4±6] In this respect, cobalt, [1,7] zinc, [3a, b] ruthenium [4a, 7, 8] and rhodium porphyrins, [6b, 7, 9] among others, have been studied. The unique enantiomeric purity obtained for 1 (about 10 9 :1), [1] as well as its high stereochemical purity, indicates that the corresponding metal complexes of 1 are highly suitable for use in stereodifferentiation and molecular recognition reactions.…”

A Porphyrin‐Doped Polymer Catalyzes Selective, Light‐Assisted Water Oxidation in Seawater

“…[3] For example, enzymes are believed to employ synchronous protein motions to cooperatively harness reactive intermediates that are often too short-lived to be utilized in other classes of catalyst. [3][4][5] This may explain how they can catalyze some reactions that cannot be catalyzed outside of biology. The question that arises is: how can one design simple, practical abiological molecular catalysts to synchronously harness very short-lived reactive intermediates?…”