The Mechanism of Rh(I)-Catalyzed Coupling of Benzotriazoles and Allenes Revisited: Substrate Inhibition, Proton Shuttling, and the Role of Cationic vs Neutral Species.

Direct coupling of benzotriazole to unsaturated substrates such as allenes represents an atom-efficient method for the construction of biologically and pharmaceutically interesting functional structures. In this work, the mechanism of the -selective Rh complex-catalyzed coupling of benzotriazoles to allenes was investigated in depth using a combination of experimental and theoretical techniques. Substrate coordination, inhibition, and catalyst deactivation was probed in reactions of the neutral and cationic catalyst precursors [Rh(μ-Cl)(DPEPhos)] and [Rh(DPEPhos)(MeOH)] with benzotriazole and allene, giving coordination, or coupling of the substrates.

Synthesis and Ligand Properties of Chelating Bis(-heterocyclic carbene)-Stabilized Bis(phosphinidenes).

NHC-phosphinidene (NHCP) adducts are an emerging class of ligands with proven binding ability for main group and transition metal elements. They possess electron-rich P atoms with two lone pairs (LPs) of electrons, making them interesting platforms for the formation of multimetallic complexes. We describe herein a modular, high-yielding synthesis of bis(NHCP)s, starting from alkylidene-bridged bis(NHC)s ((IMe)CH; = 1,3) and triphosphirane (PDip) (Dip = 2,6-PrCH) as phosphinidene transfer reagent.

How solvents affect the stability of cationic Rh(I) diphosphine complexes: a case study of MeCN coordination.

Cationic rhodium(I) diphosphine complexes, referred to as Schrock-Osborn catalysts, are privileged homogeneous catalysts with a wide range of catalytic applications. The coordination of solvent molecules can have a significant influence on reaction mechanisms and kinetic scenarios. Although solvent binding is well documented for these rhodium species, comparative quantifications for structurally related systems are not available to date.

Catalyst Deactivation During Rhodium Complex-Catalyzed Propargylic C-H Activation.

Detailed mechanistic investigations on our previously reported synthesis of branched allylic esters by the rhodium complex-catalyzed propargylic C-H activation have been carried out. Based on initial mechanistic studies, we present herein more detailed investigations of the reaction mechanism. For this, various analytical (NMR, X-ray crystal structure analysis, Raman) and kinetic methods were used to characterize the formation of intermediates under the reaction conditions.

Exploring the Phase-Selective, Green, Hydrothermal Synthesis of Upconverting Doped Sodium Yttrium Fluoride: Effects of Temperature, Time, and Precursors.

The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF with suitable dopants while adhering to the "green chemistry" standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb and Er ions were chosen as dopants for the NaYF material.