Orbital-Driven Insights into Enantioselective Hydrofunctionalization of Alkenes Catalyzed by Co-Salen Complexes: Study on Singlet and Triplet States.

The Co(salen) ([LCo(II)]) mediated hydrofunctionalization of alkenes is a highly significant method for forming enantioselective products. In this work, we conducted comprehensive computational investigations to gain insights of the reaction mechanism. The orbital analysis and intrinsic bond orbital analysis (IBO) were utilized to unravel the flow of electrons during the progress of the reaction.

Metal-free Borylation of α-Naphthamides and Phenylacetic Acid Drug.

Site-selective C-H borylation is an important strategy for constructing molecular diversity in arenes and heteroarenes. Although transition-metal-catalyzed borylation is well explored, developing metal-free strategies remains scarce. Herein, we developed a straightforward approach for BBr-mediated selective C-H borylation of naphthamide and phenyl acetamide derivatives under metal-free conditions.

Unidentical Twins: Geometrically Similar but Chemically Distinct Metal-Free Sites in Boron Oxide for Methane Oxidation to HCHO, CO and CO.

Metal-free boron-based catalysts such as boron oxide (BO) and boron nitride (h-BN) are promising catalysts for methane oxidation to HCHO and CO. The BO catalyst contains various probable boron sites (B to B), which may be responsible for methane oxidation. In this work, we utilized density functional theory to compare two relevant geometrically identical boron sites (B and B) for their reactivities.

Mapping the Catalytic-Space for the Reactivity of Metal-free Boron Nitride with O for HO-Mediated Conversion of Methane to HCHO and CO.

Transition-metal based catalysts have been widely employed to catalyze partial oxidation of light alkanes. Recently, metal-free hexagonal-boron nitride (h-BN) has emerged as a promising catalyst for the oxidation of CH to HCHO and CO; however, the intricate catalytic surface of h-BN at molecular and electronic levels remains inadequately understood. Key questions include how electron-deficient boron atoms in h-BN reduce O, and whether the partial oxidation of methane over h-BN exhibits similarities to traditional transition-metal catalysts.

Orbital Analysis Captures the Existence of a Mixed-Valent Cu -O-Cu Active-Site and its Role in Water-Assisted Aliphatic Hydroxylation.

The Cu-O-Cu core has been proposed as a potential site for methane oxidation in particulate methane monooxygenase. In this work, we used density functional theory (DFT) to design a mixed-valent Cu -O-Cu species from an experimentally known peroxo-dicopper complex supported by N-donor ligands containing phenolic groups. We found that the transfer of two-protons and two-electrons from phenolic groups to peroxo-dicopper core takes place, which results to the formation of a bis-μ-hydroxo-dicopper core.

A highly efficient Ti-catalyst for the deoxygenative reduction of esters under ambient conditions: experimental and mechanistic insights from DFT studies.

In this paper, we report the synthesis of dianionic amidophosphineborane-supported titanium chloride [{PhP(BH)N}CHTiCl] (1) and Ti alkyl complex [{PhP(BH)N}CHTi(CHSiMe)] (2) using a salt metathesis reaction. Ti complex 1 was obtained by the reaction of the bis-borane ligand [{PhP(BH)NH}CH] and TiCl in toluene followed by the addition of 2 equivalents of [LiN(SiMe)] at ambient temperature. Ti bis-alkyl complex 2 was isolated from the reaction of complex 1 with 2.

Hydroboration and reductive amination of ketones and aldehydes with HBpin by a bench stable Pd(II)-catalyst.

A palladium(II) complex [(κ-{1,2-CH(NCH-CHO)}Pd] (1) supported by a dianionic salen ligand [1,2-CH(NCH-CHO)] (L) was synthesised and used as a molecular pre-catalyst in the hydroboration of aldehydes and ketones. The molecular structure of Pd(II) complex 1 was established by single-crystal X-ray diffraction analysis. Complex 1 was tested as a competent pre-catalyst in the hydroboration of aldehydes and ketones with pinacolborane (HBpin) to produce corresponding boronate esters in excellent yields at ambient temperature under solvent-free conditions.

Catalytic Hydroboration and Reductive Amination of Carbonyl Compounds by HBpin using a Zinc Promoter.

The chemoselective hydroboration of aldehydes and ketones, catalyzed by Zinc(II) complexes [κ -(PyCH=NR)ZnX ] [R=CPh , X=Cl (1) and R=Dipp (2,6-diisoropylphenyl) and X=I (2)], in the presence of pinacolborane (HBpin) at ambient temperature and under solvent-free conditions, which produced the corresponding boronate esters in high yield, is reported. Zinc metal complexes 1 and 2 were derived in 80-90% yield from the reaction of iminopyridine [PyCH=NR] with anhydrous zinc dichloride in dichloromethane at room temperature. The solid-state structures of both zinc complexes were confirmed using X-ray crystallography.