We describe as eries of air-stable Ni III complexes supported by as imple,r obust naphthyridine-based ligand. Access to the high-valent oxidation state is enabled by the CF 3 ligands on the nickel, while the naphthyridine exhibits either am onodentate or bidentate coordination mode that depends on the oxidation state and sterics,a nd enables facile aerobic oxidation of Ni II to Ni III .These Ni III complexes act as efficient catalysts for photoinduced C(sp 2 )ÀHb ond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols.T his blue LED light-mediated catalytic protocol proceeds via ar adical pathwaya nd demonstrates potential in the late-stage functionalization of drug analogs.

Herein, we describe the first transition-metal-free catalytic carboalkoxylation of styrenes with aryl diazonium salts by Meerwein addition in the presence of a phenalenyl ligand at room temperature without requiring any light stimulation. This three-component reaction allows facile difunctionalization of styrene derivatives with various alcohols (such as 1, 2, and 3°) as the source of alkoxy group during this transformation. The key intermediates and the transition states involved in this reaction path were unraveled by a series of control experiments coupled with density functional theory calculations. The full mechanistic investigation provides an understanding of the selectivity toward carboalkoxylation (Meerwein arylation addition elimination) in the presence of various alcohols over the simple arylation to multiple bond (Meerwein arylation–elimination) reaction.

We describe a “ligand-free” Ni-catalyzed perfluoroalkylation of heteroarenes to produce a diverse array of pentafluoroethyl and heptafluoropropyl adducts. Catalysis proceeds at room temperature via a radical pathway. The catalytic protocol...

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Oxamidato-bridged Re(I)-based hexanuclear trigonal prisms with ester functionality have been synthesised via a multicomponent self-assembly process under solvothermal conditions. The self-assembly of Re2(CO)10, oxamide ligands (H2L1 = N,N′-dibutyloxamide, H2L2 = N,N′-dioctyloxamide, H2L3 = N,N′-didodecyloxamide and H2L4 = N,N′-dibenzyloxamide) and phenyl-1,3,5-tris(isonicotinate) (ptin) resulted in the formation of metallaprisms with the general formula [{(CO)3Re(μ–η(4)-L)Re(CO)3}3(μ3-ptin)2] (1–4). The metallaprisms 1–4 have been characterised using spectroscopic techniques, and the molecular structure of 4 has been elucidated by single-crystal X-ray diffraction methods. Investigations on the guest binding ability of 2 with a few aromatic alcohols and L-tryptophan using UV–vis and fluorescence spectroscopic titration experiments revealed strong host–guest interactions. The luminescence enhancement studies of 2 and 3 have been carried out using organic-aqueous solvent mixtures.