Premium
Dichotomy in the Reactivity of Trivalent Phosphorus Compounds Z 3 P (Z = Ph, n Bu, OR) Observed in the Photoreaction with a Ruthenium Complex
Author(s) -
Yasui Shinro,
Tsujimoto Munekazu,
Shioji Kosei,
Ohno Atsuyoshi
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301122
Subject(s) - chemistry , ruthenium , nucleophile , steric effects , reactivity (psychology) , ligand (biochemistry) , quenching (fluorescence) , medicinal chemistry , reaction rate constant , photochemistry , electron transfer , inorganic chemistry , stereochemistry , kinetics , catalysis , fluorescence , organic chemistry , pathology , medicine , biochemistry , physics , alternative medicine , receptor , quantum mechanics
Solutions of tris(2,2′‐bipyridyl)ruthenium(II) dichloride ( Ru 2+ ) and various types of trivalent phosphorus compounds Z 3 P (Z = Ph, n ‐Bu, OR; 1 ) in methanol have been photolyzed with visible light at 20 °C under an argon atmosphere, resulting in the oxidation of 1 to the corresponding pentavalent oxo compounds Z 3 PO and ligand exchange of Ru 2+ with 1. The former process takes place via single‐electron transfer (SET) from 1 to Ru 2+ in the photoexcited state, Ru 2+* , which generates the radical cation intermediate Z 3 P .+ from 1. The latter results from nucleophilic attack of 1 upon Ru 2+* . The results show that 1 can act either as an electron donor or as a nucleophile toward Ru 2+* . The rate constants for both processes are estimated. An excellent linear correlation is found between the logarithm of the SET rate and the oxidation potential for both the aromatic and aliphatic trivalent phosphorus comparison with SET quenching by amines. On the other hand, a dualparameter correlation analysis shows that the ligand exchange is regulated by both steric and electronic factor in 1 .