ISSN:
0009-2940
Keywords:
Trivalent phosphorus
;
Ruthenium
;
Photolysis
;
Electron transfer
;
Ligand exchange
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Solutions of tris(2,2′-bipyridyl)ruthenium(II) dichloride (Ru2+) and various types of trivalent phosphorus compounds Z3P (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 Z3P=O and ligand exchange of Ru2+ with 1. The former process takes place via single-electron transfer (SET) from 1 to Ru2+ in the photoexcited state, Ru2+*, which generates the radical cation intermediate Z3P.+ from 1. The latter results from nucleophilic attack of 1 upon Ru2+*. The results show that 1 can act either as an electron donor or as a nucleophile toward Ru2+*. 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.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971301122
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