Search

For the synthesis of vinyl boronate esters, the direct catalytic H 2 -acceptorless dehydrogenative boration of alkenes is one of the promising strategies. In this paper, the density functional theory method was employed to investigate the reaction mechanism of dehydrogenative boration and transfer boration of alkenes catalyzed by a zirconium complex (Cp 2 ZrH 2 ). There are two possible pathways for this reaction: the alkene insertion followed by the dehydrogenative boration (path A) and the alkene insertion after the dehydrogenative boration (path B). The calculated results showed that path A is more favorable than path B, and that the rate-determining step is the C-B coupling step with an energy barrier of 18.7 kcal/mol. The reaction modes of the C-B coupling assisted dehydrogenative boration and the alkene insertion were also discussed. These analyses reveal a novel hydrogen release behavior in dehydrogenative boration and the alkene insertion modes and sequences were proposed to be of importance in the chemoselectivity of this reaction. In addition, the X ligand effect (X = H, Cl) on the catalytic activity of the zirconium complex was explored, indicating that the H ligand could enhance the catalytic activity of the complex for styrene dehydrogenative boration.

The photodetector based on methylammonium lead iodide (MAPbI 3 ) is a promising device for wide wavelength range (380-780 nm) sensitivity. However, its industrial application is limited by the relatively low response speed to the light signal, which has received little attention. Only a few reports show low-bandwidth characteristics (less than 1 MHz at 0.1 cm 2 ). Here, when a cosolvent strategy to manipulate the thickness and the crystallinity of the MAPbI 3 film is adopted, photodetectors with a -3 dB bandwidth of 4.7 MHz are achieved (at 0.16 cm 2 photo detecting area). The performance is significantly better than most of the organic and hybrid photodetectors reported so far. Based on this photodetector and an organic light-emitting diode (OLED), an organic optocoupler system with 1 MHz response frequency is successfully set up. Our results suggest that thickness-manipulated cosolvent strategy is a promising method in high-speed MAPbI 3 -based photodetectors.

A density functional theory method was employed to investigate the mechanism of C-O bond activation of butanoic acid substrates bearing the 8-aminoquinoline (AQ) group catalyzed by Pd(OAc) 2 . The whole reaction consists of five fundamental steps: the chelation of substrate A1 , the C-H activation step, the C-N coupling step, the protodepalladation step, and the release of the final product. The calculated results indicated that the protodepalladation step is the rate-determining step with a free energy barrier of 24.3 kcal/mol. This theoretical study pointed out that the energy barriers of C-H activation in the presence and absence of AQ are 11.3 and 26.6 kcal/mol, respectively. This is to say that the installation of the AQ directing group is critical to the regioselectivity of C-H activation and the β-O elimination steps, and this reason enables selective activation of the γ C-O bond. Furthermore, this chelating functionality facilitated the protodepalladation step because the energy barrier of the protodepalladation step was decreased with the coordination of the AQ directing group with a Pd center, and that was 39.3 kcal/mol in the absence of AQ. This also explains why no product formation was observed in the experiment upon changing the directing AQ group to a phenylamino group. Finally, other substrates bearing the phenol leaving group at the β- and δ-positions of carbonyl were investigated in order to expand the applicability of the AQ directing strategy. This work could provide new theoretical insights into the activation of strong alkyl C(sp 3 ) covalent bonds via the AQ directing strategy.

In this paper, the mechanism of asymmetric amination of a racemic alcohol with Ellman's sulfinamide and the origin of diastereoselectivity catalyzed by a Ru-PNP pincer complex were studied using density functional theory (DFT). The mechanism involves dehydrogenation of the racemic alcohol, C-N coupling, and hydrogen transfer from the catalyst to the in situ formed imine. The calculated results indicate that both the alcohol dehydrogenation and imine hydrogenation are stepwise. The hydride transfer from a Ru hydride complex to the imine is shown to be the chirality-determining step in the whole catalytic cycle. It was found that the diastereoselectivity mainly stems from the hydrogen bonding interactions between the oxygen atom of the sulfinyl moiety and the hydrogen atom of the NH group of the ligand.