The synthesis and study of a series of pseudohalides of boron subphthalocyanine (BsubPc) are reported. Each pseudohalide has been compared to the more common chloride and bromide of BsubPc, and we have found that most react slower under standard phenoxylation and hydrolysis conditions. Three pseudohalides (TsO-BsubPc, MsO-BsubPc, and BsO-BsubPc) do not hydrolyze at all even after prolonged periods of time in the presence of water. Single crystals of TsO-, MsO-, and ClsO-BsubPc were obtained, and their structures were unambiguously determined.
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http://dx.doi.org/10.1021/jo202365x | DOI Listing |
Dalton Trans
November 2024
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
The carbene-stabilised beryllium Grignards [(CAAC)BeBrR] (R = CAACH 1a, Dur 1b; CAAC/H = 1-(2,6-dipropylphenyl)-2,2,4,4-tetramethylpyrrolidin-2-yl/idene; Dur = 2,3,5,6-tetramethylphenyl) undergo salt metathesis with various pseudohalide salt precursors. Whereas with [NaNCS] the thiocyanato Grignards [(CAAC)Be(NCS)R] (R = CAACH 2a, Dur 2b) are obtained selectively, salt metatheses with [Na(OCP)(dioxane)] and [K(OCN)] are fraught with side reactions, in particular scrambling of both neutral and anionic ligands, leading to complex product mixtures, from which the first examples of beryllium phosphaethynolate Grignards [(thf)(CAACH)Be(OCP)] (3) and [(CAAC)Be(OCP)R] (R = CAACH 4a, Dur 4b), as well as the isocyanate-bridged hexamer [(CAAC)BrBe(1,3-μ-OCN)] (7) were determined as the main products. The complexity of possible side reactions is seen in complex 5, a byproduct of the salt metathesis of 1b with [Na(OCP)(dioxane)], which hints at radical redox processes, OCP homocoupling, OCP coupling with CAAC, as well as OCP insertion into the Be-R bond.
View Article and Find Full Text PDFInorg Chem
October 2024
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstr. 2, 04103 Leipzig, Germany.
Halogenated -dodecaborates are very robust and versatile weakly coordinating anions for numerous applications. The introduction of additional substituents, e.g.
View Article and Find Full Text PDFJ Org Chem
May 2024
Institute of Chemistry of Organometallic Compounds (CNR-ICCOM), 50019 Sesto Fiorentino, Italy.
We report an efficient procedure to carry out palladium-catalyzed Miyaura borylation reactions of (hetero)aromatic halides and triflates in choline chloride (ChCl)-based deep eutectic solvents (DESs). The procedure employs bis(pinacolato)diboron as a boron source and a catalyst prepared in situ from readily available Pd(dba) and the phosphine ligand XPhos. Reactions proceed well in different ChCl-based DESs, among which the best results were provided by environmentally friendly and biodegradable mixtures with glycerol and glucose.
View Article and Find Full Text PDFDalton Trans
March 2024
Institute of Inorganic Chemistry of the Czech Academy of Sciences, Hlavní 1001, Husinec-Řež 25068, Czech Republic.
Carbon substituted cobalt bis(dicarbollide) alkyl halides [(1-X-(CH)-1,2-CBH)(1,2-CBH)-3,3'-Co]MeN (X = Br, I; = 1-3) are prepared in high yields (>90%) from their corresponding alcohols without side skeletal substitutions. These species offer access to the synthesis of aromatic cobalt bis(dicarbollide) amines, however only for particular terminal halogen substitution, the propylene pendant arm, and under appropriately controlled reaction conditions. Thus, the compounds substituted at cage carbon atoms with a propylene linker and terminal aromatic amine groups could be prepared.
View Article and Find Full Text PDFScience
March 2024
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.
The Suzuki-Miyaura and Buchwald-Hartwig coupling reactions are widely used to form carbon-carbon (C-C) and carbon-nitrogen (C-N) bonds, respectively. We report the incorporation of a formal nitrene insertion process into the Suzuki-Miyaura reaction, altering the products from C-C-linked biaryls to C-N-C-linked diaryl amines and thereby joining the Suzuki-Miyaura and Buchwald-Hartwig coupling pathways to the same starting-material classes. A combination of a bulky ancillary phosphine ligand on palladium and a commercially available amination reagent enables efficient reactivity across aryl halides and pseudohalides, boronic acids and esters, and many functional groups and heterocycles.
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