Under mild conditions, PPO-PEO-PPO ("reverse Pluronics") and PBO-PEO-PBO copolyether were generated by way of N-heterocyclic olefin-based organocatalysis. Reverse Pluronics with molar masses > 20 000 g mol could be synthesized with excellent control (Đ ≤ 1.03) and were converted into (ordered) mesoporous carbons via organic self-assembly to showcase the need for tailor-made copolymer as structure-directing agent.

Two N-heterocyclic phosphines with exocyclic SCN substituents were synthesised via metathesis of chlorophosphine precursors with KSCN and fully characterised. The crystallographic studies reveal that the products exhibit pronounced structural differences. The thiocyanato unit binds in one case via the nitrogen atom to yield a molecular structure with a slightly elongated P–N single bond and, in the other case, via the sulfur atom to form a structure that is best described as an ion pair and forms a one-dimensional coordination polymer in the crystal. DFT calculations suggest that the P–N and P…S interactions can be described as covalent and dative bonds, respectively, and that the structural differences correlate with the different cation stabilities of the individual phosphenium cation fragments.

Metathesis of Na[Mn(CO) 5 ] with N-tBu and N-Mes substituted, electrophilic N-heterocyclic phosphane derivatives afforded in the first case an ionic N-heterocyclic phosphenium (NHP) metalate and in the second case a covalent phosphenium complex. The products were characterized by analytical and spectroscopic data and the NHP complex as well by a single-crystal X-ray diffraction study. A DFT Zeitschrift für anorganische und allgemeine Chemie ARTICLE identical to those of 2c (ν = 2019, 1937, 1903 cm -1 ), [6] and their position reflects the strong π acceptor character of the NHP ligand.