Photochemical formation and reversible base-induced cleavage of a phosphagallene.

The reactivity of Cp*Ga (Cp* = CMe) towards phosphanylidenephosphoranes of the type TerP(PMe) (Ter = Ter 2,6-(2,6-iPrCH)CH), Ter 2,6-(2,4,6-iPrCH)CH was investigated. While no thermal reaction was observed (in line with DFT results), irradiation at 405 nm at low temperatures resulted in the formation of phosphagallenes TerP = GaCp* (1a) and TerP = GaCp* (1b) accompanied by release of PMe. When warming the reaction mixture to ambient temperatures without irradiation, the clean re-formation of TerP(PMe) and Cp*Ga in a second-order reaction was observed.

1-[(Methyl-sulfon-yl)-oxy]pyridin-1-ium methane-sulfonate.

The title mol-ecular salt, CHNOS·CHOS, consists of a cationic sulfonated pyridine -oxide moiety and a methane-sulfonate anion. An N-O bond length of 1.4004 (15) Å is observed in the cation.

Photomediated Hydro- and Deuterodecarboxylation of Pharmaceutically Relevant and Natural Aliphatic Carboxylic Acids.

Herein, we report a photomediated hydro- and deuterodecarboxylation of different primary, secondary, and tertiary carboxylic acids catalyzed by an organic pyrimidopteridine photoredox catalyst. The reaction was optimized by a statistical design of experiment (DoE). Under optimized reaction conditions, the conversion of commercially available nonsteroidal anti-inflammatory drugs (NSAIDs) in tablet form and on gram scale was realized.

Pyrimidopteridine-catalyzed Photo-mediated Hydroacetoxylation.

Herein we report a photo-mediated formal addition of carboxylic acids to activated alkenes catalyzed by a pyrimidopteridine photoredox catalyst. The decarboxylation of aliphatic carboxylic acids upon single-electron oxidation is countered in the presence of electron-rich alkenes and a hydroacetoxylation is observed. Mechanistic proposals have been made based on CV measurements, competitive Stern-Volmer quenching and EPR experiments.

Synthesis, Coordination Chemistry, and Mechanistic Studies of P,N-Type Phosphaalkene-Based Rh(I) Complexes.

The synthesis of P,N-phosphaalkene ligands, py-CH═PMes* (, py = 2-pyridyl, Mes* = 2,4,6-Bu-CH) and the novel quin-CH═PMes* (, quin = 2-quinolinyl) is described. The reaction with [Rh(μ-Cl)cod] produces Rh(I) bis(phosphaalkene) chlorido complexes and with distorted trigonal bipyramidal coordination environments. Complexes and show a pronounced metal-to-ligand charge transfer (MLCT) from Rh into the ligand P═C π* orbitals.

Terphenyl(bisamino)phosphines: electron-rich ligands for gold-catalysis.

Terphenyl(bisamino)phosphines have been identified as effective ligands in cationic gold(i) complexes for the hydroamination of acetylenes. These systems are related to Buchwald phosphines and their steric properties have been evaluated. Effective hydroamination was noted even at low catalyst loadings and a series of cationic gold(i) complexes has been structurally characterized clearly indicating stabilizing effects through gold-arene interactions.

Palladium-Catalyzed Synthesis of ,Dimethylanilines via Buchwald-Hartwig Amination of (Hetero)aryl Triflates.

This work delineates the synthesis of ,-dimethylaniline derivatives from dimethylamines and aryl triflates. The palladium-catalyzed C-N bond formation proceeds in excellent yields, using an unsophisticated catalytic system, a mild base, and triflates as electrophiles, which are readily available from inexpensive phenols. ,Dimethylanilines are multifunctional reaction partners and represent useful but underutilized building blocks in organic synthesis.