Reaction of cobalt porphycene with hydride reagents: spectroscopic detection of Co–H porphycene species and formation of Co–SnR3 porphycene species

Abstract

The reaction of tetrapropylporphycenatocobalt(III) with tributyltin hydride generates a cobalt(III)–hydride porphycene detectable by UV-vis spectroscopy under diluted conditions, whereas it is impossible to characterize hydride species of cobalt porphyrins. One of the reasons for the stability of the porphycene hydride species is that the porphycene ring has a lower LUMO energy level due to the decrease in the symmetry of the ligand character. However, the hydride species in a highly concentrated solution of the complex is easily converted into the cobalt(II) species via dimerization or reaction of the hydride with excess tributyltin hydride through hemolysis of the Sn–H/Co–H bonds. When the Co(III) porphycene is reacted with LiBHEt3 , the final product is the cobalt(III)–ethyl complex formed by β-rearrangement during the reaction of the hydride species and diethylborane in a solvent cage. In the reaction of tetrakistrifluoromethylporphycenatocobalt(III) with tributyltin hydride, the dominant reaction pathway includes one-electron reduction of the porphycene ring together with radical coupling of the tin reagent rather than the net hydride transfer. This finding suggests that the delicate control of the LUMO energy level influences the stability of the hydride species. The tetrapropylporphycenatocobalt(III) complex with tributyltin or triphenyltin hydride in the presence of AIBN produces the corresponding Co(III)– trialkyltin complex. This complex was characterized by 1H NMR spectroscopy.