N1,N2-diphenylacenaphthylene-1,2-diimines (BIANs) have been used to reduce the undesired high viscosity of alkyl magnesium solutions, which are known to form polymeric structures. In order to understand the mechanisms, analyses of the BIAN alkyl magnesium solutions have been carried out under inert conditions with SEC-MS, NMR, and FTIR and were compared to the structures obtained from HPLC-MS, FTIR, and NMR after aqueous workup. While viscosity reduction was shown for all BIAN derivatives used, only the bis (diisopropyl)-substituted BIAN could be clearly assigned to a single reaction product, which also could be reused without loss of efficiency or decomposition. All other derivatives have been shown to behave differently, even under inert conditions, and decompose upon contact with acidic solvents. While the chemical reactions observed after the workup of the used BIANs are dominated by (multiple) alkylation, mainly on the C = N double bond, the observation of viscosity reduction cannot be assigned to this reaction alone, but to the interaction of the nitrogen atoms of BIANs with the Mg of the alkyl magnesium polymers, as could be shown by FTIR and NMR measurements under inert conditions.

We communicate a general method for the syntheses of acenaphthene-fused imidazolinium salts that are direct precursors to augmented N-heterocyclic carbenes with a fixed cis geometry. Reduction of bis(imino)acenaphthene ligands with a LiAlH4/AlCl3 reagent mix initially produced the corresponding 1,2-diamines which, upon ring-closing reaction with triethyl orthoformate in acidic solution, gave the requisite ionic intermediates. Formation of the carbenes was then shown by preparation of selected [Cu(NHC)] complexes that were obtained via treatment of the respective imidazolinium salt with base in the presence of a Cu(I) source.