sp3 C-H bond activation with ruthenium(II) catalysts and C(3)-alkylation of cyclic amines

A selective C(3)-alkylation via activation/functionalization of sp(3) C-H bond of saturated cyclic amines was promoted by (arene)ruthenium(II) complexes featuring a bidentate phosphino-sulfonate ligand upon reaction with aldehydes. This highly regioselective sustainable transformation takes place via initial dehydrogenation of cyclic amines and hydrogen autotransfer processes.     

Autocatalysis for C-H bond activation by ruthenium(II) complexes in catalytic arylation of functional arenes

Kinetic data for the C-H bond activation of 2-phenylpyridine by Ru(II)(carboxylate)(2)(p-cymene) I (acetate) and I' (pivalate) are available for the first time. They reveal an irreversible autocatalytic process catalyzed by the coproduct HOAc or HOPiv (acetonitrile, 27 °C). The overall reaction is indeed accelerated by the carboxylic acid coproduct and water. It is retarded by a base, in agreement with an autocatalytic process induced by HOAc or HOPiv that favors the dissociation of one carboxylate ligand from I and I' and consequently the ensuing complexation of 2-phenylpyridine (2-PhPy). The C-H bond activation initially delivers Ru(O(2)CR)(o-C(6)H(4)-Py)(p-cymene) A or A', containing one carboxylate ligand (OAc or OPiv, respectively). The overall reaction is accelerated by added acetates. Consequently, C-H bond activation (faster for acetate I than for pivalate I') proceeds via an intermolecular deprotonation of the C-H bond of the ligated 2-PhPy by the acetate or pivalate anion released from I or I', respectively. The 18e complexes A and A' easily dissociate, by displacement of the carboxylate by the solvent (also favored by the carboxylic acid), to give the same cationic complex B(+) {[Ru(o-C(6)H(4)-Py)(p-cymene)(MeCN)](+)}. Complex B(+) is reactive toward oxidative addition of phenyl iodide, leading to the diphenylated 2-pyridylbenzene.     

Ferroelectric phase transition in deuterated dihydrogen phosphate,studied by infrared spectroscopy

Abstract

The temperature dependence of polar phonon spectra of K(H_1?X D_X)₂ PO₄ single crystal with x = 0.9 for the electric field polarised parallel and perpendicular to the ferroelectric axis is reported between 7 and 300 K, in the para- and ferroelectric phase.     

Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles

Ruthenium(II) complexes containing the pentamethylcyclopentadienyl ligand efficiently perform the activation of allylic carbonates and halides to generate cationic and dicationic ruthenium(IV) complexes. This activation has been transferred as a key step to the catalytic allylation of nucleophiles. The structural and electronic properties of the allylic moieties lead to the regioselective formation of chiral products resulting from nucleophilic addition to their most substituted terminus. The catalytic activity of various Ru(Cp*) precatalysts in several allylic substitutions by C and O nucleophiles will be presented. The enantioselective version that has been demonstrated by using optically pure bisoxazoline ligands will also be discussed.     

Random Repeated Interaction Quantum Systems

We consider a quantum system \({\mathcal{S}}\) interacting sequentially with independent systems \({\mathcal{E}_m}\) , m = 1,2,... Before interacting, each \({\mathcal{E}_m}\) is in a possibly random state, and each interaction is characterized by an interaction time and an interaction operator, both possibly random. We prove that any initial state converges to an asymptotic state almost surely in the ergodic mean, provided the couplings satisfy a mild effectiveness condition. We analyze the macroscopic properties of the asymptotic state and show that it satisfies a second law of thermodynamics. We solve exactly a model in which \({\mathcal{S}}\) and all the \({\mathcal{E}_m}\) are spins: we find the exact asymptotic state, in case the interaction time, the temperature, and the excitation energies of the \({\mathcal{E}_m}\) vary randomly. We analyze a model in which \({\mathcal{S}}\) is a spin and the \({\mathcal{E}_m}\) are thermal fermion baths and obtain the asymptotic state by rigorous perturbation theory, for random interaction times varying slightly around a fixed mean, and for small values of a coupling constant.     

Application de la G.P.C. a l'etude de la distribution moleculaire de polyesters non-lineaires

Molecular distribution of stoichiometric copolycondensate trimethylolpropane/azelaïc acid with conversion is investigated. Weight fractions of the first oligomers determined by G.P.C. agree with theoretical forecasts.     

Acoustic streaming related to minor loss phenomenon in differentially heated elements of thermoacoustic devices

It is demonstrated that the differentially heated stack, the heart of all thermoacoustic devices, provides a source of streaming additional to those associated with Reynolds stresses in quasi-unidirectional gas flow. This source of streaming is related to temperature-induced asymmetry in the generation of vortices and turbulence near the stack ends. The asymmetry of the hydrodynamic effects in an otherwise geometrically symmetric stack is due to the temperature difference between stack ends. The proposed mechanism of streaming excitation in annular thermoacoustic devices operates even in the absence of thermo-viscous interaction of sound waves with resonator walls.