Configurationally labile enantioenriched lithiated 3-arylprop-2-enyl carbamates: joint experimental and quantum chemical investigations on the equilibrium of epimers.

Experimental investigations as well as high-level quantum chemical calculations are performed on the two epimeric pairs of complexes 4.2 and 6.2 obtained by lithiation of cinnamyl carbamate (1) and 1-naphthyl derivative 5 in the presence of BOX ligands (S,S)- and (R,R)-2.

Effects of London dispersion on the isomerization reactions of large organic molecules: a density functional benchmark study.

A benchmark set of 24 isomerization reactions of large organic molecules (consisting of 24 to 81 atoms) is presented (termed ISOL). The molecules are much larger than what is typically considered in thermochemical tests. To obtain reference isomerization energies, complete basis set (CBS) extrapolations at the (SCS)-MP2 level have been computed that are augmented by perturbative third-order corrections (SCS-MP3 and MP2.

Configurationally labile lithiated O-benzyl carbamates: application in asymmetric synthesis and quantum chemical investigations on the equilibrium of diastereomers.

The title compounds were generated by deprotonation of different benzyl-type carbamates with sec-butyllithium in the presence of chiral diamines (-)-sparteine or diisopropyl and di-tert-butyl bis(oxazoline)s. These lithiated species exhibit configurational lability at -78 degrees C. In the case of the chiral di-tert-butyl bis(oxazoline), the equilibrium of the epimeric complexes can be used synthetically to obtain highly enantioenriched secondary benzyl carbamates.

Trinuclear copper complexes with triplesalen ligands: geometric and electronic effects on ferromagnetic coupling via the spin-polarization mechanism.

A series of trinuclear Cu(II) complexes with the tris(tetradentate) triplesalen ligands H(6)talen, H(6)talen(tBu(2) ), and H(6)talen(NO(2) ), namely [(talen)Cu(II) (3)] (1), [(talen(tBu(2) ))Cu(II) (3)] (2), and [(talen(NO(2) ))Cu(II) (3)] (3), were synthesized and their molecular and electronic structures determined. These triplesalen ligands provide three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone. The structure of [(talen)Cu(II) (3)] (1) was communicated recently.