| The homogeneous photochemical functionalization of alkanes and ethers utilizing polyoxometalates as catalysts is examined. The isopolytungstate, W{dollar}sb{lcub}10{rcub}{dollar}O{dollar}sb{lcub}32{rcub}sp{lcub}4-{rcub}{dollar}, catalyzes the photochemical functionalization of the strained caged hydrocarbon heptacyclo{dollar}rm lbrack 6.6.0.0sp{lcub}2,6{rcub}.0sp{lcub}3,13{rcub}.0sp{lcub}4,11{rcub}.0sp{lcub}5,9{rcub}.0sp{lcub}10,14{rcub}{dollar}) tetradecane, commonly referred to as HCTD, under anaerobic conditions to produce the heptacyclo{dollar}rm lbrack 6.6.0.0sp{lcub}2,6{rcub}.0sp{lcub}3,13{rcub}.0sp{lcub}4,11{rcub}.0sp{lcub}5,9{rcub}.0sp{lcub}10,14{rcub}{dollar}) tetradecyl methyl ketone derivative. The effects of several variables are examined for maximization of product yield. Several experiments are in accord with the unprecedented C-C bond forming step being the generation and capture of small quantities of HCTD carbanion by the nitrile carbon followed by protonation and hydrolysis to yield HCTD methyl ketone product. The major products generated by the anaerobic photochemical activation of adamantane, cubane, and cyclohexane by decatungstate will be discussed. The anaerobic photocatalytic oxidation of tetrahydrofuran, THF, is examined with both polyoxometalates and the semiconductor, tungstic oxide. The principal products were found to be alkene, methyl ketone, and dimer derivatives of THF. Similarities and differences in the homogeneous polyoxometalate systems and the heterogeneous semiconductor system are discussed. The anaerobic photochemical reaction of cyclooctane by {dollar}rm Qsb4Wsb{lcub}10{rcub}Osb{lcub}32{rcub}{dollar} with Pt(0) produces principally cyclooctene and coupling products. The product distribution for anaerobic photochemical cross-coupling of THF and cyclooctane by {dollar}rm Qsb4Wsb{lcub}10{rcub}Osb{lcub}32{rcub}{dollar} with the addition of Pt(0) is examined producing the major cross-coupling product, the tetrahydrofuryl-cyclooctyl derivative.; Formed easily by the mixture of an organic substrate, 1,1,3,3-tetramethylurea (TMU), and the heteropolymolybdic acid, {dollar}alpha{dollar}-{dollar}rm Hsb3PMosb{lcub}12{rcub}Osb{lcub}40{rcub}{dollar}, the resulting complex, ((TMU){dollar}sb2{dollar}H) {dollar}sb3{dollar}PMo{dollar}sb{lcub}12{rcub}{dollar}O{dollar}sb{lcub}40{rcub}{dollar}, was characterized by X-ray crystallography. Several polyoxotungstates (HPA-23, SiW{dollar}sb{lcub}12{rcub}{dollar}O{dollar}sb{lcub}40{rcub}sp{lcub}4-{rcub}{dollar}, and BW{dollar}sb{lcub}12{rcub}{dollar}O{dollar}sb{lcub}40{rcub}sp{lcub}5-{rcub}){dollar} were synthesized, characterized, and examined as HIV-1 antiviral agents. HPA-23 was extensively studied by {dollar}sp{lcub}183{rcub}{dollar}W NMR. Since sterically hindered porphyrins are useful in homogeneous oxygenation and biomimetic studies, the synthesis of the sterically hindered porphyrin tetrakis(2,6-dichlorophenyl)porphyrin, TDCPP, is examined. |
