Bounds to average interelectronic angles in Hartree-Fock theory of atoms

The average interelectronic is the expectation value of the angle thetaij (0 < or = thetaij < or = pi) subtended by the position vectors ri and rj of a pair of electrons i and j. In the Hartree-Fock theory of atoms, we point out that the angle and its subshell-pair components nl,n'l' are bounded from above and below, where n and l are the principal and azimuthal quantum numbers. The upper bounds for nl,n'l' with 0 < or = l, l' < or = 3 are 9pi/16 (=101.25 degrees), 135pi/256 (approximately 94.922 degrees), 265pi/512 (approximately 93.164 degrees), and 129pi/256 (approximately 90.703 degrees) for sp, pd, df, and sf pairs, respectively, while they are pi/2 (=90 degrees ) for the other ll' pairs, independent of n and n'. A weighted sum of these subshell-pair bounds gives an upper bound to . The lower bounds are pi/2 in all the cases.     

Chirality exchange from sp3 central chirality to axial chirality: benzannulation of optically active diaryl-2,2-dichlorocyclopropylmethanols to axially chiral alpha-arylnaphthalenes

Chirality exchange benzannulation of optically active (1S)-aryl(aryl')-2,2-dichlorocyclopropylmethanols (>99% ee) using TiCl4 successfully proceeded to give axially chiral (M)-alpha-arylnaphthalenes with excellent levels of stereo induction (>99% ee). This unique transformation involves the single-step chirality exchange from sp3 central chirality to axial chirality, that is, a type of excellent memory effect.     

Relativistic correlating basis sets for 57La and 89Ac

Developed and reported are compact yet efficient correlating basis sets for the ₅₇La and ₈₉Ac atoms, missing in the literature. Good performance of these correlating sets is exemplified in molecular applications to diatomic oxides and fluorides. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Molecular structures and magnetic properties of the mixed-ligand complexes of bis(hexafluoroacetylacetonato)manganese(II), -copper(II), and -zinc(II) with 4,4'-bis(N-tert-butyl-N-oxylamino)-2,2'-bipyridine. Isosceles triangular hetero-three-spin systems consisting of aminoxyls and metal ions

4,4'-Bis(N-tert-butyloxylamino)-2,2'-bipyridine (4) and its 1:1 complexes with bis(hexafluoroacetylacetonato)manganese(II), -copper(II), and -zinc(II) were prepared. An X-ray structure analysis of free ligand 4 reveals that the molecule has a trans conformation with Ci symmetry and the aminoxyl radical center has a short contact of 2.36 A with one of the neighboring molecules. The three 1:1 complexes have mutually similar molecular structures in which the 2,2'-bipyridine moiety has a cis conformation and serves as a bidentate ligand and coordination geometry around the metal atom is a distorted octahedron. The EPR experiments for free ligand 4 and [Zn(hfac)2.4] in frozen solution suggested that the exchange couplings between the two aminoxyls (R) through the 2,2'-bipyridine rings are antiferromagnetic with JR-R/kB = -19.3 +/- 0.5 and -24.3 +/- 0.4 K, respectively. Isosceles triangular three-spin models were applied to the 1:1 magnetic metal complexes to give JR-M/kB = -19.1 +/- 0.2 K and JR-R/kB = -32.9 +/- 0.3 K for [Mn(hfac)2.4] and JR-M/kB = +73 +/- 18 K and JR-R/kB = -24.5 +/- 6.5 K for [Cu(hfac)2.4].     

Podophyllotoxin aza-analogue, a novel DNA topoisomerase II inhibitor

The pendant E-ring moiety of the podophyllotoxin aza-analogue 1 that is a potent inhibitor of microtubule assembly was modified in order to acquire inhibitory activity of DNA topoisomerase II. The monophenolic analogue 2 did not exhibit human topoisomerase II inhibition, while the ortho-quinone 3 that was obtained by oxidation of 2 inhibited its catalytic activity (decatenation) in a dose-dependent manner and stimulated double strand DNA breaks in supercoiled circular plasmid DNA, resulting in the production of linear DNA. These results showed that the topoisomerase II inhibition of the ortho-quinone 3 is due to stabilization of the topoisomerase II-DNA covalent binary complex. On the other hand, the ortho-quinone 3 did not inhibit the relaxation process of supercoiled DNA by topoisomerase I at concentrations up to 400 microM, nor was intercalation observed in unwinding measurements of 3. Therefore, the ortho-quinone 3 was shown to be a novel nonintercalative topoisomerase II specific inhibitor that stabilizes the cleavable complex. The present results suggest that the 4'-free hydroxyl group on the E-ring and the sugar moiety on the C-ring are not a prerequisite for topoisomerase II inhibition by podophyllotoxin derivatives.     

New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Reaction of selenobenzophenones with olefins. Formation of 1H-2-benzoselenopyrans. Reaction of 1H-2-benzoselenopyrans with diazoalkanes

Selenobenzophenone reacts as a diene with dimethyl acetylenedicarboxylate (DMAD) to lead to dimethyl 1H-1-diphenylmethyl-1-phenyl-2-benzoselenopyran-3,4-dicarboxylate (5c) in moderate yield; the initial [4 + 2] cycloaddition is followed by the addition of another 1 mol equiv of selenobenzophenone. The reaction might proceed through carbene insertion of the primary cycloadduct. On the other hand, 4,4'-dimethoxyselenobenzophenone combines as a diene with DMAD furnishing dimethyl 1H-1-p-methoxyphenyl-6-methoxy-2-benzoselenopyran-3,4-dicarboxylate (4a). The reaction of benzoselenopyran derivative (4) with diaryldiazomethanes afforded another type of carbene insertion product.     

Kinetic Analysis of the Thermal Decomposition of Synthetic Malachite by CRTA

The kinetic behavior of the thermal decomposition of synthetic malachite was investigated by means of CRTA under different conditions of reduced pressure, flowing gases and quasi-isobaric atmospheres. The thermal decomposition was found to proceed at lower temperatures under the influence of the self-generated gases, CO₂ and H₂O. From a viewpoint of chemical equilibrium, the normal and opposite effects on the overall kinetics were observed for the self-generated CO₂ and H₂O, respectively. The complexity of the present reaction is also reflected by the variations of the apparent kinetic parameters which depend on the applied and self-generated atmospheric conditions. The practical usefulness of CRTA when applied to a complicated thermal decomposition is discussed as exemplified by the kinetic approaches to the present reaction. This revised version was published online in August 2006 with corrections to the Cover Date.