Acrolein [KLH]

Highly conjugated perinones were evaluated as proligands with [Ru(eta(6)-arene)Cl-2](2) precursors (arene = p-cymene or benzene). None of them, except itaco-perinone (IP) bearing one exocyclic methylene group, were able to form coordination compounds. Expected eta(1)-coordination through the lone pair of the nitrogen or oxygen atoms of the perinone did not occur. Instead a deprotonation reaction involving the exocyclic methylene was observed and the corresponding [Ru(eta(6)-arene)(eta(3)-IP)Cl] complex was isolated in moderate yields. Mechanistic studies revealed that the base-promoted isomerization of itaco-perinone to citraco-perinone prevented higher yields in the synthesis of the allylic complexes. Additionally, it was observed that IP can dimerize through the exocyclic methylene group, indicating high reactivity of this carbon-carbon double bond. Electronic absorption and emission properties of the perinones and organometallic compounds were studied.

Glycerol is a major by-product of biodiesel production and has attracted great interest as a precursor for the preparation of various valuable chemicals. Conversion of glycerol over alpha-Fe2O3 catalyst in a fixed-bed flow reactor was investigated to understand the catalytic activity of iron oxide for the selective production of allyl alcohol. Addition of formic acid to the glycerol feed was effective in improving allyl alcohol production because decomposition on the catalyst formed hydrogen atoms, which were consumed in dehydroxylation of glycerol and reduction of alpha-Fe2O3 to Fe3O4 during glycerol conversion. Moreover, the allyl alcohol yield was further increased using potassium-loaded alpha-Fe2O3 catalyst, which was attributed to change in the acid sites. The original acid sites of alpha-Fe2O3, mainly Lewis acid sites, were occupied by potassium, and Bronsted acid sites formed during glycerol conversion. To further enhance the allyl alcohol yield, we attempted to minimize the polymerization reaction by optimizing the potassium loading, W-cat/F-glycerol value (i.e., contact time), and reaction temperature. The highest allyl alcohol yield of 39.8 C-mol% was achieved over 1 mol% potassium-loaded alpha-Fe2O3 at 623 K and with W-cat /F-glycerol of 1 h.