High-pressure metathesis was proposed to be a gateway to the elusive class of rare-earth nitridophosphates. With this method the first ternary compounds of this class with sum formula RE2P3N7 were prepared, a melilite-type with RE = Pr, Nd, Sm, Eu, Ho, Yb (Ho2P3N7: P4̅21m, a = 7.3589(2), c = 4.9986(2) Å, Z = 2) and a Ba2Cu[Si2O7] structure type with RE = La, Ce, Pr (Pr2P3N7: monoclinic, C2/c, a = 7.8006(3), b = 10.2221(3), c = 7.7798(3) Å, β = 111.299(1)°, Z = 4). The phase relation between the two structure types was prior unknown and is here evidenced by experimental data as well as density functional theory calculations performed for the Pr2P3N7 compounds. Adequate classification of both structures types with regard to Liebau nomenclature, vertex symbol, and point symbol is made. Additionally, the tiling patterns of the monolayered structures are deducted. We demonstrate that high-pressure metathesis offers a systematic access to rare-earth nitridophosphates with an atomic ratio of P/N between 1/2 and 1/4.

The first sodiations of (hetero)arenes in continuous flow using NaDA (sodium diisopropylamide) in Me EtN are reported. This flow procedure enables sodiation of functionalized arenes and heteroarenes that decompose under batch-sodiation conditions. The resulting sodiated (hetero)arenes react instantly with various electrophiles, such as ketones, aldehydes, isocyanates, alkyl bromides, and disulfides, affording polyfunctionalized (hetero)arenes in high yields. Scale-up is possible without further optimization.

Rare-earth nitridophosphates are a recently discovered class of materials, which are accessible by high-pressure metathesis. Antiperovskite-type Ho 3 [PN 4 ]O was synthesized from HoF 3 , LiPN 2 , Li 3 N, and Li 2 O at 5 GPa and ca. 1025°C by this method and the multianvil technique. Ho 3 [PN 4 ]O contains rarely observed isolated PN 4 tetrahedra and can be derived by the hierarchical substitution of the ABX 3 perovskite, in which Ho occupies the X positions, O occupies the B position, and the PN 4 tetrahedra occupy the A position. The structure was refined on the basis of powder diffraction data [I4/mcm, a = 6.36112(3), c = 10.5571(1) Å, Z = 4, R wp = 0.04, R Bragg = 0.01, 2 = 2.275] starting from the structural model of isotypic Gd 3 [SiN 3 O]O. To characterize Ho 3 [PN 4 ]O, elemental analyses were performed [a]

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We report a halogen-lithium exchange performed in the presence of various metal salts (ZnCl , MgCl ⋅LiCl) on a broad range of sensitive bromo- or iodo(hetero)arenes using BuLi or PhLi as the exchange reagent and a commercially available continuous-flow setup. The resulting diarylmagnesium or diarylzinc species were trapped with various electrophiles, resulting in the formation of polyfunctional (hetero)arenes in high yields. This method enables the functionalization of (hetero)arenes containing highly sensitive groups such as an isothiocyanate, nitro, azide, or ester. A straightforward scale-up was possible without further optimization.