The Reactivity Of singlet carbenes. An ab initio study

The energy barriers for the addition to ethylene of a series of carbenes have been calculated at an ab initio level. using the STO-3G and 3-21G basis sets. It is shown that the usual extrapolation of experiment results, which predicts that the reactivity of carbenes decreases when increasing its nucleophilic character, is not valid.     

Single and double metallic layer-containing ruthenium dendrimers. Synthesis and catalytic properties

The reaction of a series of phosphanyl-terminated carbosilane dendrimers displaying only one phosphorus ligand per arm with [RuCl(2)(p-cymene)](2) resulted in the grafting of RuCl(p-cymene) moieties on the periphery of the dendrimer. In these species, the chloride ligand is easily displaced by the organic bases pyridine, 4-cyanopyridine and 4,4[prime or minute]-bipyridine to afford new cationic metallodendrimers. NMR studies have confirmed the chirality of the ruthenium centre. The species containing 4,4[prime or minute]-bipyridine reacts through the uncoordinated pyridyl nitrogen with a new equivalent of [RuCl(2)(p-cymene)](2) or [RhCl(CO)(2)](2) to lead to homo- or hetero-bimetallic layer-containing dendrimeric systems. The ruthenodendrimers were tested as catalysts in the transfer hydrogenation of cyclohexanone by propan-2-ol and their activity compared with that of some analogous mononuclear ruthenium(ii) complexes.     

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order M?ller-Plesset perturbation theory, fourth-order M?ller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values.     

Variational transition state theory as a tool to determine kinetic selectivity in reactions involving a valley-ridge inflection point

Variational transition state theory has been used to calculate the kinetic isotope effects affecting product ratios in the reaction between (1)O(2) and d(6)-tetramethylethylene. The minimum energy path on the potential energy surface for this process reaches a valley-ridge inflection point and then bifurcates leading to the two final products. Using canonical variational transition state theory, two distinct dynamical bottlenecks were located corresponding to the H- and the D-abstraction, respectively. The calculated KIE at 263 K turns out to be 1.126. Analogously, a H/T KIE of 1.17 at the same temperature has been found for the reaction of (1)O(2) with the tritiated derivative of tetramethylethylene.     

Unprecedented eight-palladium(I) crown-cycle with metal-metal unsupported bonds

Tri(N-pyrrolyl)phosphine reacted with the sigma/pi complex [Pd(mu-Cl)(COD-MeO)]2 to give the octa-cycle [Pd(mu-Cl)[P(pyrl)3]]8 containing four Pd(I)-Pd(I) unbridged bonds.     

Modular amino alcohol ligands containing bulky alkyl groups as chiral controllers for Et2Zn addition to aldehydes: illustration of a design principle

A new family of enantiomerically pure (1S,2R)-1-alkyl-2-(dialkylamino)-3-(R-oxy)-1-propanols containing a very bulky alkyl substituent (tert-butyl or 1-adamantyl) on their hydrocarbon chains has been synthesized from the corresponding enantiopure epoxy alcohols, arising from the catalytic Sharpless epoxidation, by protection of the primary hydroxy group and subsequent regioselective ring opening of the epoxide by a secondary cyclic amine (C-2 attack). The performance of these amino alcohols as ligands for the catalytic enantioselective addition of diethylzinc to benzaldehyde has been studied, with enantioselectivities of 92-96% being recorded. The best performing ligands, those with a bulky R-oxy group, also depict a convenient activity and selectivity profile in the addition of Et(2)Zn to a representative family of aldehydes. An anomalous structure/enantioselectivity relationship of some ligands in the tert-butyl series has been studied using PM3 calculations, and conclusions have been drawn on the possible effects of including in modular designs structural fragments giving rise to a variety of rotameric transition states.     

Structure and dynamics of dense monolayers of no adsorbed on Rh(111) in equilibrium with the gas phase in the Torr pressure range

Using scanning tunneling microscopy, we show the phase transition between new structures of NO on Rh(111) in equilibrium with the gas phase near 300 K, in the Torr pressure range. Two phases with (2 x 2) and (3 x 3) periodicity transform into each other as the pressure and temperature change around the equilibrium P-T line. By measuring P and T at coexistence, we determined the heat of adsorption in the (3 x 3) structure. From the phase boundary dynamics, the activation energy barrier between phases were estimated. The results demonstrate that unique information can be obtained from high-pressure and high-temperature studies.     

Dynamics of layering transitions in confined liquids

Multiple beam interferometry and video microscopy were used to investigate the layering transition of thin liquid films of 1-undecanol confined between atomically smooth mica surfaces. The expulsion of a molecularly thin lubricant layer was followed directly in two dimensions. Overall, the dynamics of the transition follows theoretical predictions based on two-dimensional hydrodynamics. Frequently, pockets of liquid remain trapped inside the contact area at the end of the transition. The trapped pockets undergo shape transformations to minimize elastic and interfacial energy.