We have used dispersion-corrected DFT (DFT-D) together with solvation to examine possible mechanisms for reaction of PhX (X = Cl, Br, I) with Pd(P(t)Bu(3))(2) and compare our results to recently published kinetic data (F. Barrios-Landeros, B. P. Carrow and J. F. Hartwig, J. Am. Chem. Soc., 2009, 131, 8141-8154). The calculated activation free energies agree near-quantitatively with experimental...

N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions m...

Fisher-Hartwig asymptotics refers to the large n form of a class of Toeplitz determinants with singular generating functions. This class of Toeplitz determinants occurs in the study of the spin-spin correlations for the two-dimensional Ising model, and the ground state density matrix of the impenetrable Bose gas, amongst other problems in mathematical physics. We give a new application of the o...

5-pyrrolidino-m-terphenyl (1) is synthesized via a Buchwald-Hartwig cross-coupling reaction. This terphenyl readily halogenated under ambient conditions with tetrabutylammonium tribromide to generate 4-pyrrolidino-2,6-diphenylbromobenzene (2). The reaction of (2) magnesium results in the conversion its corresponding Grignard reagent (3). Quenching (3) water recovery (1), demonstrating ability r...

The paper is devoted to exact and asymptotic formulas for the determinants of Toeplitz matrices with perturbations by blocks of fixed size in the four corners. If the norms of the inverses of the unperturbed matrices remain bounded as the matrix dimension goes to infinity, then standard perturbation theory yields asymptotic expressions for the perturbed determinants. This premise is not satisfi...