Oxidation of primary and secondary benzylic alcohols with hydrogen peroxide and tert-butyl hydroperoxide catalyzed by a "helmet" phthalocyaninato iron complex in the absence of added organic solvent.

The oxidation of four benzylic alcohols employing hydrogen peroxide and TBHP as oxidants, catalyzed by an iron(III) complex bearing a 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand has been studied and found to proceed with good selectivity, high turnover numbers, and high turnover frequencies in the absence of organic solvents other than the substrates themselves.

Resolution of enantiomers of a series of chiral alkoxy-modified phthalocyaninato nickel(II) complexes by enantioselective HPLC.

We have resolved the enantiomers of a series of chiral modified metallophthalocyaninato complexes of nickel bearing alkoxy groups at the 14 and 28 positions on what would otherwise be a normal phthalocyaninato ligand and conforming to the general formula [14,28-(RO)(2)Pc]Ni(ii), where R = Me, Et, or n-Pr. The complex for which R = n-Pr is reported here for the first time. Resolution of the enantiomers of these complexes was accomplished via HPLC utilizing an immobilized carbohydrate-based stationary phase, resulting in baseline resolution of peaks corresponding to enantiomers of the complexes, with R(s) values in excess of five. Isolation of milligram quantities of the complexes bearing methoxy and n-propoxy groups in high enantiomeric excess has been achieved via semi-preparative-scale HPLC on the same stationary phase. Resolved samples of these compounds do not appear to racemize at an appreciable rate, nor do they readily exchange alkoxy groups with alcohols while stirring in alcoholic solution. The spectroscopic details and the crystallographically-determined solid-state structure for the complex where R = n-Pr are reported, and are highly similar to those that have been observed for the previously reported analogues. It has been shown by NMR that the chirality and C(2) molecular symmetry of the complex bearing n-propoxy groups is maintained in solution.

Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex.

We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.

Constructor graph description of hydrogen bonding in a supramolecular assembly of N,N'-bis(2-hydroxy-1-methylethyl)phthalamide.

Hydrogen bonds of four types (N-H...O=C, N-H...OH, O-H...O=C and O-H...OH) connect molecules of the title compound, C(14)H(20)N(2)O(4), in the crystal into sheets folded into a zigzag pattern. The intermolecular interactions are discussed in terms of the first- through fourth-level graph sets, and a constructor graph helps visualize the supramolecular assembly.

Racemic iron(III) and cobalt(III) complexes containing a new pentadentate "helmet" phthalocyaninato ligand.

Solvothermal reactions of iron(II) acetate tetrahydrate and cobalt(II) acetate tetrahydrate with 1,2-dicyanobenzene in methanol solution result in the formation of racemic six-coordinate iron(III) and cobalt(III) complexes, respectively, with a new bicyclic pentadentate 14,28-[1,3-diiminoisoindolinato]phthalocyaninato ligand.

Why magnesium is five-coordinate in methanol(phthalocyaninato)magnesium(II).

The square-pyramidal Mg center in the title compound, [Mg(C(32)H(16)N(8))(CH(4)O)], is five-coordinate due to the formation of back-to-back pi-pi dimers that saturate the vacant apical site of the metal coordination sphere. Each complex is a member of a back-to-back and a face-to-face dimer; the latter are tethered by two strong O-H...N hydrogen bonds. The dimers form columns that likely determine the solid-state packing. The phthalocyaninate ligands are essentially planar, with a slight 'hat visor' conformation character.