Facile methyl group transfer from Pt to gallium and indium.

Facile transmetalation is observed from a d metal, platinum(II), to indium and gallium leading to the extrusion of methylated gallate and indate anions representing a rare case of the "reverse" transmetalation from a d metal to a main group metal. The Pt-Ga and Pt-In bonding in the bimetallic complexes was analyzed through bosonic and fermionic potentials, QTAIM, and NBO.

Facile Access to Cationic Methylstannylenes and Silylenes Stabilized by E-Pt Bonding and their Methyl Group Transfer Reactivity.

We describe a family of cationic methylstannylene and chloro- and azidosilylene organoplatinum(II) complexes supported by a neutral, binucleating ligand. Methylstannylenes MeSn: are stabilized by coordination to Pt and are formed by facile Me group transfer from dimethyl or monomethyl Pt complexes, in the latter case triggered by concomitant B-H, Si-H, and H bond activation that involves hydride transfer from Sn to Pt. A cationic chlorosilylene complex was obtained by formal HCl elimination and Cl removal from HSiCl under ambient conditions.

Transforming atmospheric CO into alternative fuels: a metal-free approach under ambient conditions.

This work demonstrates the first-ever completely metal-free approach to the capture of CO from air followed by reduction to methoxyborane (which produces methanol on hydrolysis) or sodium formate (which produces formic acid on hydrolysis) under ambient conditions. This was accomplished using an abnormal N-heterocyclic carbene (NHC)-borane adduct. The intermediate involved in CO capture (NHC-H, HCOO, B(OH)) was structurally characterized by single-crystal X-ray diffraction.

Phenalenyl Based Aluminum Compound for Catalytic C-H Arylation of Arene and Heteroarenes at Room Temperature.

Main group metal based catalysis has been considered to be a cost-effective alternative way to the transition metal based catalysis, due to the high abundance of main group metals in the Earth's crust. Among the main group metals, aluminum is the most abundant (7-8%) in the Earth's crust, making the development of aluminum based catalysts very attractive. So far, aluminum based compounds have been popularly used as Lewis acids in a variety of organic reactions, but chemical transformation demanding a redox based process has never utilized an Al(III) complex as a catalyst.

Halo-Bridged Abnormal NHC Palladium(II) Dimer for Catalytic Dehydrogenative Cross-Coupling Reactions of Heteroarenes.

This work describes the dehydrogenative coupling of heteroarenes using a dimeric halo-bridged palladium(II) catalyst bearing an abnormal NHC ( aNHC) backbone. The catalyst can successfully activate the C-H bond of a wide range of heteroarenes, which include benzothiazole, benzoxazole, thiophene, furan, and N-methylbenzimidazole. Further, it exhibited good activity for heteroarenes bearing various functional groups such as CN, CHO, Me, OMe, OAc, and Cl.

Metal-Free Reduction of CO to Methoxyborane under Ambient Conditions through Borondiformate Formation.

An abnormal N-heterocyclic carbene (aNHC) based homogeneous catalyst has been used for the reduction of carbon dioxide to methoxyborane in the presence of a range of hydroboranes under ambient conditions and resulted in the highest turnover number of 6000. A catalytically active reaction intermediate, [aNHC-H⋅9BBN(OCOH) ] was structurally characterized and authenticated by NMR spectroscopy. A detailed mechanistic cycle of this catalytic process via borondiformate formation has been proposed from tandem experimental and computational experiments.