Grapperhaus Craig A, Ouch Kagna, Mashuta Mark S
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
J Am Chem Soc. 2009 Jan 14;131(1):64-5. doi: 10.1021/ja8086483.
The influence of oxidation state on the reversibility of carbon-sulfur bond forming reactions between ethylene and Re(DPPBT)(3) (n = 0, +1, +2; DPPBT = 2-diphenylphosphinobenzenethiolate) has been investigated. For the neutral complex [Re(DPPBT)(3)], no reaction with ethylene is spectroscopically detectable consistent with the determined equilibrium constant, K(1), of (1.9 +/- 0.4) x 10(-11) M(-1). Oxidation by one electron to Re(DPPBT)(3) yields a stable complex that rapidly and reversibly binds ethylene with electrochemically determined constants of k(f) = (1.2 +/- 0.2) x 10(-1) M(-1) s(-1), k(r) = (3.0 +/- 0.4) x 10(-2) s(-1), and K(2) = 4.0 +/- 0.8 M(-1). C-S bond formation/cleavage can be regulated by ethylene concentration, and the system is stable to multiple cycles of nitrogen/ethylene purges. Further oxidation to the dication in the presence of ethylene by chemical or electrochemical methods stabilizes the C-S bond, K(3) = (2.5 +/- 0.9) x 10(9) M(-1), and the dithioether product has been characterized by X-ray crystallography. The large differences in K as a function of charge permit the controlled binding and release of ethylene as a function of applied potential.
