Synthesis, Structure, and Reactions of Iridium (I) Complexes with 5,10,15,20-Tetraphenyl-21H, 23H-Porphine and 5,10,15,20-Tetraphenyl-21H,23H-Porphine Dianion

摘要

One-step joint synthesis of two iridium porphyrin complexes, a donor—acceptor SAT (sitting a top) complex μ-(5,10,15,20-tetraphenylporphine)-bis-chloroiridium(I) and the covalent complex (5,10,15,20-tetraphenylporphinato)chloroiridium(III) by the reaction of free porphyrin and chloroiridic acid (H_3O)_2IrCl_6 in boiling phenol was studied. The structure of complexes was confirmed by spectroscopy (UV/Vis, IR, ~1H NMR) and TLC. The iridium(III) SAT complex with the hydride ligand in the first coordination sphere, (acetato)hydrido(5,10,15,20-tetraphenylporphine)iridium(III), was obtained by oxidative addition reaction, which is quite rare for porphyrin complexes. The thermodynamic stability of the complexes to oxidants (aerated acids) was studied by spectrophotometric titration.