Metal Fluorides Passivate II-VI and III-V Quantum Dots.

Quantum dots (QDs) with metal fluoride surface ligands were prepared via reaction with anhydrous oleylammonium fluoride. Carboxylate terminated II-VI QDs underwent carboxylate for fluoride exchange, while InP QDs underwent photochemical acidolysis yielding oleylamine, PH3, and InF3. The final photoluminescence quantum yield (PLQY) reached 83% for InP and near unity for core-shell QDs. Core-only CdS QDs showed dramatic improvements in PLQY, but only after exposure to air. Following etching, the InP QDs were bound by oleylamine ligands that were characterized by the frequency and breadth of the corresponding ν(N-H) bands in the infrared absorption spectrum. The fluoride content (1.6-9.2 nm-2) was measured by titration with chlorotrimethylsilane and compared with the oleylamine content (2.3-5.1 nm-2) supporting the formation of densely covered surfaces. The influence of metal fluoride adsorption on the air stability of QDs is discussed.

Ligand-based control of nuclearity in (NHC)gold(I) sulfides.

N-Heterocyclic carbene (NHC) ligands support gold(I) sulfide complexes of varying nuclearity and charge. For sterically undemanding ligands, gold(I) chlorides react with sulfide to form trigold µ3-sulfido cations as the first observed products. The ligand IMes [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] supports a monomeric cation, whereas the ICy-(1,3-dicyclohexylimidazol-2-ylidene-) supported cation crystallises as a dimer linked through an aurophilic interaction. The more sterically demanding IDipp [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] supports a terminal hydrosulfide, a (µ-hydrosulfido)digold cation, and a µ3-sulfido cation. Use of the expanded-ring NHC 7Dipp [1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene] allows the isolation of a neutral digold sulfide.

Nitrosonium Reactivity of (NHC)Copper(I) Sulfide Complexes.

This study examines the reactivity of a series of copper(I) sulfide complexes stabilized by the expanded-ring N-heterocyclic carbene (NHC) 1,3-bis(2,6-diisopropylphenyl)-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene (7Dipp) toward the nitrosonium ion (NO+). 7Dipp is shown to support neutral sulfide- and disulfide-bridged dicopper(I) complexes, as well as mononuclear copper(I) hydrosulfide. The addition of NO+ to each of these results in the formation of NHC-supported copper(I) cations and elemental sulfur. Reduction of copper(I) to copper(0) is observed upon reaction of NO+ with dicopper(I) sulfide or disulfide, whereas ammonium ion formation is observed upon reaction of copper(I) hydrosulfide with NO+. Ammonium ion formation is likewise observed upon reaction of NO+ with (7Dipp)copper(I) hydride.

Copper(I)-Mediated Borofluorination of Alkynes.

The electrophilic fluorination of N-heterocyclic carbene (NHC) copper(I) vinyls results in fluoroalkene formation. Alkynes can be converted to cis-(ß-fluorovinyl)boronates by a reaction with an (NHC)copper(I) boryl generated in situ, followed by N-fluorobenzenesulfonimide (NFSI). This sequence gives rise to anti-Markovnikov fluorination products from terminal alkynes. Oxidation of a cis-(ß-fluorovinyl)trifluoroboronate yields an α-fluoroketone, whereas a palladium-catalyzed Suzuki-Miyaura coupling yields a tetrasubstituted monofluoroalkene.

Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity.

Hydride complexes of copper, silver, and gold encompass a broad array of structures, and their distinctive reactivity has enabled dramatic recent advances in synthesis and catalysis. This Review summarizes the synthesis, characterization, and key stoichiometric reactions of isolable or observable coinage metal hydrides. It discusses catalytic processes in which coinage metal hydrides are known or probable intermediates, and presents mechanistic studies of selected catalytic reactions. The purpose of this Review is to convey how developments in coinage metal hydride chemistry have led to new organic transformations, and how developments in catalysis have in turn inspired the synthesis of reactive new complexes.

Synthesis of 2-amino-imidazo[4,5-b]pyridines.

The C2 amination of imidazo[4,5-b]pyridines was accomplished through C2 halogenation followed by substitution (SNAr) with functionalized primary and secondary amines. This regioselective sequence is operationally simple and provides an easy access to derivatives of protected imidazo[4,5-b]pyridines.