Description: This article discusses single-electron oxidation of monomeric copper(I) alkyl complexes. Monomeric Cu(I) alkyl complexes (NHC)Cu(R) (NHC = N-heterocyclic carbene; R = Me or Et) and (dtbpe)Cu(Me) (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) have been prepared, isolated, and characterized. Single-electron oxidation of the Cu(I) alkyl complexes upon reaction with AgOTf to form putative Cu(II) intermediates of the type [(L)Cu(R)]+ (L = NHC or dtbpe, R = Me or Et) results in the rapid production of (L)Cu(X) (X = OTf) and R2. Experimental studies suggest that the reductive elimination of R2 from Cu(II) occurs through a nonradical bimolecular mechanism. Computational studies of the Cu-Cmethyl yield bond dissocation enthalpies of [(SIPr)Cu-CH3]n+ (80 kcal/mol for n = 0 {Cu(I)} and 38 kcal/mol for n = 1 {Cu(II)}).

Description: This article discusses six-, five-, and four-coordinate ruthenium(II) hydride complexes. The Ru(II) hydride complex (IMes)2Ru(Cl)(H)(CO) (1) {IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene} was synthesized from [Ru(CO)2Cl2]n and free IMes. Complex 1 rapidly reacts with CO to produce the cis-dicarbonyl Ru(II) complex (IMes)2Ru(Cl)(H)(CO)2 (2). The reaction of 1 with NaBAr'4 {Ar' = 3,5-(CF3)C6H3} produces the four-coordinate Ru(II) cationic complex [(IMes)2Ru(H)(CO)][BAr'4] (4), which can be trapped by two equivalents of tert-butylisonitrile to produce [(IMes)2Ru(H)(CO)(CNtBu)2][BAr'4] (5). Experimental and computational studies suggest that complex 4 is a diamagnetic system that adopts a sawhorse structure. The hydride ligand of complex 2 is readily displaced as dihydrogen upon reaction with HCI to produce (IMes)2Ru(CI)2(CO)2 (3). Both complex 1 and 4 were found to react with D2 (30 psi) at room temperature to produce the isotopomers (IMes)2Ru(CI)(D)(CO) (1-d1) and [(IMes)2Ru(D)(CO)][BAr'4] (4-d1), respectively, with the rate of formation of 4-d1 at least 28 times faster than the conversion of 1/D2 to 1-d1. In the presence of excess D2 complex 4 reversibly incorporates deuterium into the ortho methyl groups of the IMes ligands, whereas complex 1 does not show evidence of H/D exchange with the IMes ligands. Both 1 and 4 were found to catalyze the hydrogenation of olefins, ketones, and aldehydes.

Description: This article presents a study of the influence of solar activity on the earth's temperature. In particular, the authors focus on the repercussion of the fluctuations of the solar irradiance on the temperature of the Northern and Southern hemispheres as well as on land and ocean regions. While solar irradiance data are not directly analyzed, the authors make use of a published solar irradiance reconstruction for long-time-scale fluctuations, and for short-time-scale fluctuations the authors hypothesize that solar irradiance and solar flare intermittency are coupled in such a way that the solar flare frequency fluctuations are stochastically equivalent to those of the solar irradiance. The analysis is based upon wavelet multiresolution techniques and scaling analysis methods for processing time series. The limitations of the correlation analysis applied to the short-time-scale fluctuations are discussed. The scaling analysis uses both the standard deviation and the entropy of the diffusion generated by the temperature signals. The joint use of these two scaling methods yields evidence of a Levy component in the temporal persistence of the temperature fluctuations within the temporal range from a few weeks to a few years. This apparent Levy persistence of the temperature fluctuations is found, by using an appropriate model, ...

Description: This article discusses the solubility of phenylacetic acid in binary solvent mixtures. Abstract: Solubilities are reported for phenylacetic acid at 25.0 °C in binary mixtures of carbon tetrachloride with cyclohexane, n-heptane, n-octane, or isooctane and mixtures of cyclohexane with n-heptane or isooctane. The results are compared to the predictions of equations developed previously for solubility in systems of purely nonspecific interactions, with phenylacetic acid considered as either monomeric or dimeric molecules in solution. The dimer model provided the more accurate predictions and described the 15-fold range of solubilities in the carbon tetrachloride + isooctane system to within a maximum deviation of 15%.

Description: This article discusses the solubility of pyrene in binary solvent mixtures containing dibutyl ether. Experimental solubilities are reported for pyrene in binary solvent mixtures containing dibutyl ether with n-hexane, cyclohexane, n-heptane, methylcyclohexane, n-octane, isooctane, and tert-butylcyclohexane at 26 °C. Results of these measurements, combined with estimates for the excess Gibbs free energies of the binary solvents, are used to test predictive expressions derived from the nearly ideal binary solvent (NIBS) model. Expressions based on a volume fraction average of solute properties in the two pure solvents predict pyrene solubilities to within a maximum deviation of 10% and an overall average deviation of 3.2%.