Synthesis, reactivity, and ligand properties of a stable alkyl carbene

Stable tert-butyl diisopropylamino carbene is more nucleophilic but also more electrophilic than diamino carbenes; it undergoes cyclopropanation reactions and easily binds to metal fragments.     

Micro-Raman investigations of the formaldehyde-ice system

Rapidly frozen aqueous solutions containing variable amounts of dissolved formaldehyde (0.1, 5, 7, 10, 15, and 20 mol %) have been analyzed by micro-Raman spectroscopy at ambient pressure and low temperature. The importance of the formladehyde-ice system has been repeatedly quoted in various contexts, such as atmospheric and snowpack chemistry and interstellar and cometary ices. Understanding and characterizing the effects of freezing and the interactions of formaldehyde with ice are therefore of relevant interest. In this study, the distinct vibrational signatures of the oligomers present in the solution and in the frozen ice mixtures have been identified in the 120-4000 cm(-1) spectral range. From the subtle changes of the bands assigned to the CO and CH group frequencies, at least two distinct crystalline phases (pI and pII) are found to coexist with ice at different temperatures. Depending on the cooling-rewarming protocol, pI is found to crystallize in the 163-213 K temperature range. Above approximately 213 K, pI gets transformed irreversibly into pII which is stable up to approximately 234 K. pII is found to interact more strongly with ice than pI, as revealed, for example, by the drop in frequency of the bands assigned to the O-H stretching as pI transforms into pII. It is suggested that pII consists of a hydrogen-bonded network of oligomers and water molecules. On the other hand, it is suggested that the oligomers mainly present in pI interact through weak forces with the surrounding water molecules.     

Nonperturbative fixed point in a nonequilibrium phase transition

We apply the nonperturbative renormalization group method to a class of out-of-equilibrium phase transitions (usually called "parity-conserving" or, more properly, "generalized voter" class) which is out of the reach of perturbative approaches. We show the existence of a genuinely nonperturbative fixed point, i.e., a critical point that does not seem to be Gaussian in any dimension.     

Theory of spin hall conductivity in n-doped GaAs

We develop a theory of extrinsic spin currents in semiconductors, resulting from spin-orbit coupling at charged scatterers, which leads to skew-scattering and side-jump contributions to the spin-Hall conductivity. Applying the theory to bulk n-GaAs, without any free parameters, we find spin currents that are in reasonable agreement with experiments by Kato et al. [Science 306, 1910 (2004)].     

Long-range critical wetting: observation of a critical end point

Alkanes deposited on aqueous substrates exhibit two different types of wetting behavior: alternatively to the usual first-order wetting transition, a sequential-wetting scenario of a long-range critical wetting transition preceded by a first-order thin-thick transition may be observed. Here, we present the first successful experimental attempt to locate the transition point between the standard first-order wetting and the long-range critical wetting: a critical end point, observed in a mixture of pentane and hexane which is deposited on an aqueous solution of glucose. Furthermore, we present the first direct measurement of the contact angle in the intermediate wetting state (frustrated-complete wetting) in the sequential-wetting scenario of hexane on brine and compare to theoretical predictions.     

Nonperturbative renormalization-group study of reaction-diffusion processes

We generalize nonperturbative renormalization group methods to nonequilibrium critical phenomena. Within this formalism, reaction-diffusion processes are described by a scale-dependent effective action, the flow of which is derived. We investigate branching and annihilating random walks with an odd number of offspring. Along with recovering their universal physics (described by the directed percolation universality class), we determine their phase diagrams and predict that a transition occurs even in three dimensions, contrarily to what perturbation theory suggests.     

Amino-aryl-carbenes: alternative ligands for transition metals?

Despite the presence of a single amino substituent, an amino-anthryl-carbene was found to behave as a strong sigma-donor weak pi-acceptor ligand toward rhodium(I) fragments.     

Thiyl radical-mediated cleavage of allylic C-N bonds: scope, limitations, and theoretical support to the mechanism

Thiols mediate the radical isomerization of allylic amines into enamines. The reaction results in the cleavage of the allylic C-N bond, after treatment with aqueous HCl. The mechanism involves the abstraction of an allylic hydrogen alpha to nitrogen by thiyl radical, followed by a return hydrogen transfer from the thiol to the carbon gamma to nitrogen in the intermediate allylic radical. The scope and limitations of the reaction with respect to the nature of the thiol, to the structure of the allylic chain, and to the nature of the substituents at nitrogen were investigated. The experimental results were interpreted on the ground of DFT calculations of the C-Halpha BDE in the starting allylic amines, and of the C-Hgamma BDE in the resulting enamines. The efficiency of the initial hydrogen transfer is the first requirement for the reaction to proceed. A balance must be found between the S-H BDE and the two above-mentioned C-H BDEs. The incidence of stereoelectronic factors was analyzed through NBO calculations performed on the optimized geometries of the starting allylic amines. Additional calculations of the transition structures and subsequent tracing of the reaction profiles were performed for the abstraction of Halpha from both the allyl and the prenyl derivatives by p-TolS(*). The latter allowed us to estimate the rate constant for the abstraction of hydrogen by thiyl radical from an N-prenylamine and an N-allylamine.     

Theoretical study of rhodium(I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes

Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.