Catalytic asymmetric hydrogenation with the cluster Rh6(CO)10[(-)DIOP]3

Rh₆(CO)₁₀[(-)DIOP]₃ has been isolated after ligand exchange between Rh₆(CO)₁₆ and DIOP. The molecular cluster is an efficient catalyst for asymmetric reduction of various prochiral olefins; optical yields up to 47% have been achieved; the results are compared with those obtained with mononuclear rhodium (I) complexes.     

Nanocatalysts for Suzuki cross-coupling reactions

This critical review deals with the applications of nanocatalysts in Suzuki coupling reactions, a field that has attracted immense interest in the chemical, materials and industrial communities. We intend to present a broad overview of nanocatalysts for Suzuki coupling reactions with an emphasis on their performance, stability and reusability. We begin the review with a discussion on the importance of Suzuki cross-coupling reactions, and we then discuss fundamental aspects of nanocatalysis, such as the effects of catalyst size and shape. Next, we turn to the core focus of this review: the synthesis, advantages and disadvantages of nanocatalysts for Suzuki coupling reactions. We begin with various nanocatalysts that are based on conventional supports, such as high surface silica, carbon nanotubes, polymers, metal oxides and double hydroxides. Thereafter, we reviewed nanocatalysts based on non-conventional supports, such as dendrimers, cyclodextrin and magnetic nanomaterials. Finally, we discuss nanocatalyst systems that are based on non-conventional media, i.e., fluorous media and ionic liquids, for use in Suzuki reactions. At the end of this review, we summarise the significance of nanocatalysts, their impacts on conventional catalysis and perspectives for further developments of Suzuki cross-coupling reactions (131 references).     

A well-defined mesoporous amine silica surface via a selective treatment of SBA-15 with ammonia

2D double-quantum (1)H-(1)H NMR unambiguously shows that the "isolated" ≡Si-OH surface silanols of dehydroxylated SBA-15 are converted upon treatment with ammonia into single silylamine surface site ≡Si-NH(2). The "gem" di-silanols (=Si(OH)(2)) remain intact. Treatment using HMDS produces (=Si(OSiMe(3))(2)) but leaves ≡Si-NH(2) untouched. The resulting surface is hydrophobic and stable.     

A convenient access to 1,3-disubstituted furo[3,4-b]indoles by acid ion-exchange resin-catalyzed furan formation

Efficient synthesis of furo[3,4-b]indoles starting from the corresponding indole is reported. The first route involves derivatization, protection, and deprotection steps, which stretch the syntheses. The second method provides a shorter and more efficient strategy to accessing the furoindole. The innovation starts with alkylation at C-2 of the indole presenting at the C-3 position a ketone-acetal, followed by the cycloaromatization catalyzed by polymeric ion-exchange resins. The second route represents a significant improvement over other methods previously described.     

Emission and absorption quantum noise measurement with an on-chip resonant circuit

Using a quantum detector, a superconductor-insulator-superconductor junction, we probe separately the emission and absorption noise in the quantum regime of a superconducting resonant circuit at equilibrium. At low temperature the resonant circuit exhibits only absorption noise related to zero point fluctuations, whereas at higher temperature emission noise is also present. By coupling a Josephson junction, biased above the superconducting gap, to the same resonant circuit, we directly measure the noise power of quasiparticles tunneling through the junction at two resonance frequencies. It exhibits a strong frequency dependence, consistent with theoretical predictions.     

Grafting of [Mn(CH2tBu)2(tmeda)] on silica and comparison with its reaction with a silsesquioxane

The reaction of [Mn(CH2tBu)2(tmeda)] (1) and a silica partially dehydroxylated at 700 degrees C (SiO(2/700)) yields a single surface species [([triple bond]SiO)Mn(CH2tBu)(tmeda)] (2a; tmeda = tetramethylethylendiamine), while a mixture of 2a and [([triple bond]SiO)2Mn(tmeda)] (2b) is obtained by using SiO(2/200), SiO(2/300), or SiO(2/500) as evidenced by mass balance analysis, and IR and EPR spectroscopy. The reaction of 1 and (c-C5H9)7Si7O12SiOH (3), a soluble silanol that is a molecular model for a silica support, generates the bis-siloxy complex 4, [[(c-C5H9)7Si7O12SiO]2Mn(tmeda)2], in a quantitative yield; compound 4 was characterized by single-crystal X-ray diffraction. These reactions exemplify the limitation of considering molecular silanol derivatives as straightforward and reliable homogeneous models for silica, and address the need for thorough characterization of surface species by the use of surface-science techniques. These studies show the possibility of preparing coordinatively and geometrically unique surface species that would be difficult to prepare by solution chemistry methods; insights into the chemical and physical properties of these surface species are also gained.