Stereoisomers and functional groups in oxidorhenium(v) complexes: effects on catalytic activity.

The syntheses of oxidorhenium(v) complexes [ReOCl(L1a-c)2] (3a-c), equipped with the bidentate, mono-anionic phenol-dimethyloxazoline ligands HL1a-c are described. Ligands HL1b-c contain functional groups on the phenol ring, compared to parent ligand 2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-phenol H1a; namely a methoxy group ortho to the hydroxyl position (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-6-methoxyphenol, H1b), or a nitro group para to the hydroxyl position (2-(4,4-dimethyl-4,5-dihydro-1,3-oxazol-2-yl)-4-nitrophenol, H1c). Furthermore, oxidorhenate(v) complexes (NBu4)[ReOCl3(L1a-b)] (2a-b) were synthesized for solid state structural comparisons to 3a-b. All novel complexes are fully characterized including NMR, IR and UV-Vis spectroscopy, MS spectrometry, X-ray crystallography, elemental analysis as well as cyclic voltammetry. The influence of functional groups (R = -H, -OMe and -NO2) on the catalytic activity of 3a-c was investigated in two benchmark catalytic reactions, namely cyclooctene epoxidation and perchlorate reduction. In addition, the previously described oxidorhenium(v) complex [ReOCl(oz)2] (4), employing the phenol-oxazoline ligand 2-(4,5-dihydro-2-oxazolyl)phenol Hoz, was included in these catalysis studies. Complex 4 is a rare case in oxidorhenium(v) chemistry where two stereoisomers could be separated and fully characterized. With respect to the position of the oxazoline nitrogen atoms on the rhenium atom, these two stereoisomers are referred to as N,N-cis and N,N-trans isomer. A potential correlation between spectroscopic and structural data to catalytic activity was evaluated.

Iron catalyzed oxidation of benzylic alcohols to benzoic acids.

The bidentate N,O-ligands phenol-pyrazole (HL1), naphthol-pyrazole (HL2) and the commercially available ligand 5-methylphenol-benzotriazole (HL3) were used for the synthesis of novel iron(iii) complexes. The mononuclear iron complexes [FeCl(L1)2] (1), [FeCl(L2)2] (2) and [FeCl(L3)2] (3) are stable to air and moisture, both in the solid state as well as in solution, while the dinuclear, µ-oxido bridged complex [{Fe(L1)2}2(µ-O)] (1a) is air sensitive. All four complexes 1, 2, 3 and 1a were investigated for their catalytic activity in the direct one-pot oxidation of primary alcohols to carbonic acids with 30% aq. hydrogen peroxide (H2O2) as the oxidation agent. The activity in oxidation reactions of the isolated, mononuclear complexes 1-3 was further compared to their in situ prepared analogues IS1-3. Experimentally obtained results indicate a tendency of higher activity for the oxidation of primary alcohols for the in situ prepared complexes. In conclusion, the oxidation of aromatic primary alcohols to carboxylic acids using isolated iron(iii) complexes and in situ generated complexes in the presence of H2O2 results in good to high yields. The reaction is straight-forward, clean and generates water as the only by-product.

Absolute configuration in 4-alkyl- and 4-aryl-3,4-dihydro-2(1H)-pyrimidones: a combined theoretical and experimental investigation.

Structural features (orientation of the carboxyl group, ring puckering), electronic absorption, and circular dichroism spectra of 4-alkyl- and 4-aryl-dihydropyrimidones 1-5 are calculated by semiempirical (AM1, INDO/S), ab initio (HF/6-31G, CIS/6-31G, RPA/6-31G), and density functional theory (B3LYP/6-31G) methods. These calculations allow an assignment of the absolute configuration by comparison of simulated and experimental CD spectra. Although the ab initio methods greatly overestimate electronic transition energies, the general appearance of the experimental CD spectra is quite nicely reproduced by these calculations. Thus, comparison of experimental with calculated CD spectra is a reliable tool for the assignment of the absolute configuration. For 4-methyl derivatives 1, the first enantiopure DHPM examples with no additional aromatic substituent, the stereochemistry at C4 provided by the theoretical results is confirmed by X-ray structure determination of the diastereomeric salt 6. Additional support is the consistent HPLC elution order found for all investigated DHPMs on a cellulose-derived chiral stationary phase.

Triaqua(oxalato-O,O')oxovanadium(IV) dihydrate

In the structure of the title compound, [VO(C(2)O(4))(H(2)O)(3)]. 2H(2)O, the V atom of the oxovanadium(IV) cation is coordinated to one bidentate oxalate anion and three water molecules, resulting in a neutral complex. Two more water molecules are not coordinated to the V atoms but are involved in the hydrogen-bonding network, which consists of ten different hydrogen bonds.