Kinetic studies conducted under both catalytic and stoichiometric conditions were employed to investigate the reductive elimination of RuPhos (2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl) based palladium amido complexes. These complexes were found to be the resting state in Pd-catalyzed cross-coupling reactions for a range of aryl halides and diarylamines. Hammett plots demonstrated that...

The first syntheses of 4-methyl-2-t-butyland 2-methyl-4.6-di-t-butyl-indole are described. Rates of diazocoupling at the 3-position of both these compounds together with those for 2-methyland 2-t-butyl-indole are reported for various para-substituted arenediazonium ions in mixed aqueous and some aprotic solvents a t 25". The kinetic behaviour of 2-methylindole is examined in detail and it is sh...

Octahedral ruthenium complexes of the type TpRu(L)(NCMe)R [Tp ) hydridotris(pyrazolyl)borate; R ) alkyl or aryl; L ) CO or PMe3] have been shown previously to initiate the C-H activation of aromatic substrates. In order to probe the nature of the C-H activation step, reaction rates have been theoretically obtained for the conversion of TpRu(L)(η-C,C-C6H5X)Me to TpRu(L)(p-C6H4X) and CH4 where X ...

ABSTRACT The kinetics and mechanism of the aromatic nucleophilic substitution reactions of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole with para-X-substituted anilines (X = OH, OMe, Me, H, F, I, Cl) were studied in MeOH-Me2SO mixtures and pure Me2SO at 25.0 °C. The second-order rate coefficients depend on the substitutent in aniline and give good Hammett and Brønsted correlations; a polar ...

The direct quantitative correspondence between theoretical predictions and the measured plasma fluctuations and transport is tested by performing nonlinear gyro-Landau-fluid simulations with the GRYFFIN ~or ITG! code @W. Dorland and G. W. Hammett, Phys. Fluids B 5, 812 ~1993!; M. A. Beer and G. W. Hammett, Phys. Plasmas 3, 4046 ~1996!#. In an L-mode reference discharge in the DIII-D tokamak @J....

A systematic study of the dehydrogenation of substituted thiophenols by controlled charge injection from the tip of a scanning tunneling microscope (STM) reveals a pronounced dependence of the reaction yield on the position and the chemical nature of the substituent. We evaluate the dehydrogenation rate of para-halo-substituted species within a linear free energy relationship, namely the Hammet...

Raloxifene and arzoxifene are benzothiophene selective estrogen receptor modulators (SERMs) of clinical use in postmenopausal osteoporosis and treatment of breast cancer and potentially in hormone replacement therapy. The benefits of arzoxifene are attributed to improved bioavailability over raloxifene, whereas the arzoxifene metabolite, desmethylarzoxifene (DMA) is a more potent antiestrogen. ...