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Scheme 5. Hydrogen Atom Transfer from Toluene to Permanganate Oxo Ligand Scheme 6. C-H Bond Oxidation of Dihydroanthracene by a Dinuclear (µ-Oxo)Manganese Complex (L ) 1,10-phenanthroline) Scheme 7. C-H Bond Oxidation of Toluene via Initial Hydride Abstraction by Manganese(IV) Dimer [(phen) 2 Mn(µ-O) 2 Mn(phen) 2 ](ClO 4 ) 4 (L ) 1,10-Phenanthroline)

Ammonium removal from aqueous solution by a natural ion-exchange resin was investigated by considering the factors affecting the ammonium-exchange capacity including the zeolites' particle size, the loading flow rates and the impact of a number of regenerations upon the ion-exchange capacity. The resin column was exhausted by downflow at 10, 25, 50 and 75 bed volume (BV)/h, until effluent ammonium concentration of more than 10 mg/l NH 4 + was achieved. The results indicate that conditioning of the zeolite improves the ion-exchange capacity and that the smaller particle size also causes a higher ion-exchange capacity due to greater available surface area. The actual ion-exchange capacity of the conditioned fine (-1.00+0.125) and coarse (-2.00+1.00) mm clinoptilolite was found to be 0.57 and 0.38 meq/g zeolite, respectively.

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Carbon-carbon bond activation of diphenylacetylene and several substituted derivatives has been achieved via photolysis and studied. Pt0-acetylene complexes with eta2-coordination of the alkyne, along with the corresponding PtII C-C activated photolysis products, have been synthesized and characterized, including X-ray crystal structural analysis. While the C-C cleavage reaction occurs readily under photochemical conditions, thermal activation of the C-C bonds or formation of PtII complexes was not observed. However, the reverse reaction, C-C reductive coupling (PtII --> Pt0), did occur under thermal conditions, allowing the determination of the energy barriers for C-C bond formation from the different PtII complexes. For the reaction (dtbpe)Pt(-Ph)(-CCPh) (2) --> (dtbpe)Pt(eta2-PhCCPh) (1), DeltaG was 32.03(3) kcal/mol. In comparison, the energy barrier for the C-C bond formation in an electron-deficient system, that is, (dtbpe)Pt(C6F5)(CCC6F5) (6) --> (dtbpe)Pt(eta2-bis(pentafluorophenyl)acetylene) (5), was found to be 47.30 kcal/mol. The energy barrier for C-C bond formation was able to be tuned by electronically modifying the substrate with electron-withdrawing or electron-donating groups. Upon cleavage of the C-C bond in (dtbpe)Pt(eta2-(p-fluorophenyl-p-tolylacetylene) (9), both (dtbpe)Pt(p-fluorophenyl)(p-tolylacetylide) (10) and (dtbpe)Pt(p-tolyl)(p-fluorophenylacetylide) (11) were obtained. Kinetic studies of the reverse reaction confirmed that 10 was more stable toward the reductive coupling [the term "reductive coupling" is defined as the formation of (dtbpe)Pt(eta2-acetylene) complex from the PtII complex] than 11 by 1.22 kcal/mol, under the assumption that the transition-state energies are the same for the two pathways. The product ratio for 10 and 11 was 55:45, showing that the electron-deficient C-C bond is only slightly preferentially cleaved.