Gold(I)-Catalyzed Nucleophilic Propargylations of Azinium Ions via Hydroxydihydroazine Intermediates.

The nucleophilic propargylation of azinium ions with a propargylboronate proceeds efficiently under gold(I) catalysis. A range of N-alkylated pyridinium, quinolinium, and pyrazinium ions undergo propargylation with good yields and high regioselectivities to give various functionalized 1,4-dihydropyridines, 1,2-dihydropyridines, 1,4-dihydroquinolines, 1,2-dihydroquinolines, and 4,5-dihydropyrazines. No allenylation side-products are observed.

Structure and thermal stability of phosphorus-iodonium ylids.

Hypervalent iodine(III) reagents have become indispensable tools in organic synthesis, but gaps remain in the functionalities they can transfer. In this study, a fundamental understanding of the thermal stability of phosphorus-iodonium ylids is obtained through X-ray diffraction, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Insights into the structural factors affecting thermal stability and potential decomposition pathways will enable the future design and development of new reagents.

Ligand solid-solution tuning of magnetic and mechanical properties of the van der Waals metal-organic magnet NiCl(btd)(bod).

Van der Waals (vdW) magnets offer unique opportunities for exploring magnetism in the 2D limit. Metal-organic magnets (MOM) are of particular interest as the functionalisation of organic ligands can control their physical properties. Here, we demonstrate tuning of mechanical and magnetic function of a noncollinear vdW ferromagnet, NiCl(btd) (btd = 2,1,3-benzothiadiazole), through creating solid-solutions with the oxygen-substituted analogue ligand 2,1,3-benzoxadiazole (bod).

Synthesis of the Bulky Phosphanide [P(SiPr)] and Its Stabilization of Low-Coordinate Group 12 Complexes.

Here, we report an improved synthesis of the bulky phosphanide anion [P(SiPr)] in synthetically useful yields and its complexation to group 12 metals. The ligand is obtained as the sodium salt NaP(SiPr) in a 42% isolated yield and a single step from red phosphorus and sodium. This is a significantly higher-yielding and safer preparation compared to the previously reported synthesis of this ligand, and we have thus applied to the synthesis of the two-coordinate complexes M[P(SiPr)] (M = Zn, Cd, Hg).

Structural Transformations of Metal-Organic Cages through Tetrazine-Alkene Reactivity.

The assembly of metal-organic cages is governed by metal ion coordination preferences and the geometries of the typically rigid and planar precursor ligands. PdL cages are among the most structurally diverse, with subtle differences in the metal-ligand coordination vectors resulting in drastically different assemblies, however almost all rely on rigid aromatic linkers to avoid the formation of intractable mixtures. Here we exploit the inverse electron-demand Diels-Alder (IEDDA) reaction between tetrazine linker groups and alkene reagents to trigger structural changes induced by post-assembly modification.