Abstract
Extremely crowded triarylphosphines were synthesized by the reaction of arylcopper(I) reagents with chlorophosphines, and the relationship between molecular structure and redox properties was studied by X-ray crystallography and cyclic voltammetry. As the substituent on phosphorus became bulkier, bond lengths and angles around phosphorus atom became longer and larger, and oxidation potential was significantly lowered. Especially, tris(2,4,6-triisopropylphenyl)phosphine had an extremely crowded structure and was oxidized to a stable radical cation at an extraordinarily low oxidation potential. Novel redox systems possessing the crowded triarylphosphine structure as one of the redox sites were designed and synthesized.