title: Kinetics and mechanisms of catalytic oxygen atom transfer with oxorhenium(V) oxazoline complexes.
abstract: The rhenium(V) monooxo complexes (hoz)2Re(O)Cl (1) and [(hoz)2Re(O)(OH2)][OTf] (2) have been synthesized and fully characterized (hoz = 2-(2'-hydroxyphenyl)-2-oxazoline). A single-crystal X-ray structure of 2 has been solved: space group = P1, a = 13.61(2) A, b = 14.76(2) A, c = 11.871(14) A, alpha = 93.69(4) degrees, beta = 99.43(4) degrees, gamma = 108.44(4) degrees, Z = 4; the structure was refined to final residuals R = 0.0455 and Rw = 0.1055. 1 and 2 catalyze oxygen atom transfer from aryl sulfoxides to alkyl sulfides and oxygen-scrambling between sulfoxides to yield sulfone and sulfide. Superior catalytic activity has been observed for 2 due to the availability of a coordination site on the rhenium. The active form of the catalyst is a dioxo rhenium(VII) intermediate, [Re(O)2(hoz)2]+ (3). In the presence of sulfide, 3 is rapidly reduced to [Re(O)(hoz)2]+ with sulfoxide as the sole organic product. The transition state is very sensitive to electronic influences. A Hammett correlation plot with para-substituted thioanisole derivatives gave a reaction constant rho of -4.6 +/- 0.4, in agreement with an electrophilic oxygen transfer from rhenium. The catalytic reaction features inhibition by sulfides at high concentrations. The equilibrium constants for sulfide binding to complex 2 (cause of inhibition), K2 (L x mol(-1)), were determined for a few sulfides: Me2S (22 +/- 3), Et2S (14 +/- 2), and tBu2S (8 +/- 2). Thermodynamic data, obtained from equilibrium measurements in solution, show that the S=O bond in alkyl sulfoxides is stronger than in aryl sulfoxides. The Re=O bond strength in 3 was estimated to be about 20 kcal x mol(-1). The high activity and oxygen electrophilicity of complex 3 are discussed and related to analogous molybdenum systems.
authors: Department of Chemistry and Biochemistry, University of California, Los Angeles, 405 Hilgard Avenue, Los Angeles, California 90095-1569, USA.
authors: J
authors: J
authors: Arias
authors: C R
authors: CR
authors: Newlands
authors: M M
authors: MM
authors: Abu-Omar
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D007700:Kinetics; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010080:Oxazoles / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry; D013454:Sulfoxides / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D010080:Oxazoles; D013440:Sulfides; D013454:Sulfoxides; D012211:Rhenium; D010100:Oxygen