OXIDATION OF THIOLATO COMPLEXES OF RUTHENIUM(III) BY PEROXYMONOSULFATE

The HSO5- oxidation of thiols coordinated to ruthenium(III) centers proceeds cleanly via two discrete steps to give the corresponding sulfenato and sulfinato complexes. First-order behavior was observed with respect to both complex ion and oxidant. The first oxidation step is sensitive to the nature of the sulfur substituent, and rates follow a Hammett correlation with rho = -0.66. In contrast, the second reaction is relatively insensitive to the nature of the substituent. This paper describes the preparation of several (thiolato)ruthenium(III) complexes and their oxidation kinetics.