We report a general method to synthesize gold nanocrystal micelles with organo-silane headgroups. The method involves encapsulation of monodisperse, hydrophobic gold nanocrystals within the core of a micelle of an amphiphilic silane precursor. Formation and stability of monodisperse gold NC micelles have been confirmed using UV-visible spectroscopy and transmission electron microscopy. Self-ass...

The o-palladated, chloro-bridged dimers [Pd{2-phenylpyridine(-H)}-μ-Cl]2 and [Pd{N,N-dimethylbenzylamine(-H)}-μ-Cl]2 react with cyanuric acid in the presence of base to afford closed, chiral cage-molecules in which 12 organo-Pd(II) centers, located in pairs at the vertices of an octahedron, are linked by four tetrahedrally arranged cyanurato(3-) ligands. Incomplete (Pd10) cages, having structur...

The direct oxidative coupling reaction has been an attractive tool for environmentally benign chemistry. Reported herein is that the hypervalent iodine catalyzed oxidative metal-free cross-coupling reaction of phenols can be achieved using Oxone as a terminal oxidant in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP). This method features a high efficiency and regioselectivity, as well as functional-g...

The intramolecular alpha-arylation of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Selective oxidation of chiral enamines (formed by the condensation of an aldehyde and a secondary amine catalyst) leads to the formation of a 3pi-electron radical species. These chiral SOMO-activated radical cations undergo enantioselective reaction with an array of pe...

A new method to rapidly generate pyrrolidines via a SOMO-activated enantioselective (3 + 2) coupling of aldehydes and conjugated olefins has been accomplished. A radical-polar crossover mechanism is proposed wherein olefin addition to a transient enamine radical cation and oxidation of the resulting radical furnish a cationic intermediate which is vulnerable to nucleophilic addition of a tether...

Solubili t ies of silver a n d copper in the i r mol ten salt mix tu res AgCl^Bri j ; a n d C u C U B r i ^ were measured as a f unc t i on of T a n d x. F r o m the t e m p e r a t u r e dependence of t h e solubil i t ies, t h e en tha lp ies a n d ent ropies of dissolution could be ob ta ined as a func t ion of x. Unexpec t ed ly these func t ions v a r y nonmonotonous ly wi th x. The entha ...

The intramolecular alpha-arylation of aldehydes via organo-SOMO catalysis was investigated using density functional theory (B3LYP and M06-2X functionals). The geometries, spin densities, Mulliken charges, and molecular orbitals of the reacting enamine radical cations were analyzed, and the nature of the resulting cyclized radical cation intermediates was characterized. In agreement with experim...

Antimony(V) and bismuth(V) complexes of lapachol have been synthesized by the reaction of Ph₃SbCl₂ or Ph₃BiCl₂ with lapachol (Lp) and characterized by several physicochemical techniques such as IR, and NMR spectroscopy and X-ray crystallography. The compounds contain six-coordinated antimony and bismuth atoms. The antimony(V) complex is a monomeric derivative, (Lp)(Ph₃Sb)OH, and the bismuth(V) ...

Active Al, Fe and Si (i.e., oxalate extractable fraction: Alo, Feo, Sio) strongly affect soil physical, chemical biological properties. This study examined the pedogenic factors affecting Feo Sio contents across a weathering sequence in Cameroon volcanic line. We investigated B horizon (∼50-cm depth) from 26 soils formed basaltic materials at different elevations (110–2570 m) incorporating wide...

A series of fully bio-based poly(ester- alt -thioether)s are efficiently synthesized by organo-catalyzed alternating ring-opening copolymerizations eugenol-derived monomers, vanillin glycidyl ether and N -acetyl homocysteine thiolactone.