A fitting formula for the falloff curves of unimolecular reactions,II: Tunneling effects

By taking into account effects of tunneling on the shape of the falloff curves of unimolecular reaction rate constants based on Troe's weak collision integral, a fitting formula for these curves is developed and then examined for several tunneling‐affected reactions. It is demonstrated that, compared to the widely used Troe's formula, the present expression not only substantially enhances the accuracy in fitting for tunneling‐affected reactions, but it is also computationally more efficient in its evaluation. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 43: 31–42, 2011     

Synthesis and application of palladium stearates as precursors for the preparation of palladium nanoparticles

This report successfully demonstrates the synthesis and application of palladium stearates. It was found that the branching of the carboxylate anion of metal precursors could influence the size and shape of palladium nanoparticles (PdNPs). Worm‐like nanowires were formed when using the branched isomer palladium isostearate (PdISt₂), while triangular nanoparticles were produced in a majority when using the normal form: palladium stearate (PdSt₂). Furthermore, when applying CO₂ to the system, both types of PdNPs transformed into more spherical shapes with smaller sizes. The formation of carbamates from the amine stabilizer with CO₂ could prevent the further growth and aggregation of PdNPs. The PdNPs were tested as catalysts for the hydrogenation of styrene, and higher catalytic activities were achieved with PdNPs that were prepared with the assistance of CO₂. Copyright © 2012 John Wiley & Sons, Ltd.     

Phosphonium-Ring-Fused Bicyclic Metallafuran Complexes of Ruthenium and Osmium

Metallafuran complexes with a fused five-membered phosphonium ring were synthesized from reactions between terminal ynones HC≡C(C=O)R and cis-[Ru/Os(dppm)₂Cl₂] (dppm=1,1-bis(diphenylphosphino)methane). A metal–vinylidene-involving pathway was found to be an energetically feasible formation mechanism for these complexes. These phosphonium-containing metallafurans, like many phosphonium-functionalized drugs, have the ability to induce mitochondrial dysfunction. They also exhibit stronger cytotoxicity against several human cancer cell lines in comparison with their metal precursors and the classic anticancer drug cisplatin. Overall, this work provides structural and mechanistic insights for the rational design of functional metallacycles via activation of alkynes by Ru^II and Os^II centers.     

Preparation and Reaction of Cyclic Oxalate of Diols

Cyclic oxalates were efficiently prepared by the reaction of diols with ethyl oxalyl chloride in the presence of triethylamine. They were stable under acidic conditions but cleaved to diols under basic conditions.