From Bis(imidazol‐2‐yl)methanes to Asymmetrically Substituted Bis(heterocyclo)methanides in Metal Coordination

As an extension to the known symmetric bis(heterocyclo)methanes containing two identical heterocycles, new asymmetric ligand systems, based on benzoxazole, benzothiazole and 1‐methylbenzimidazole, are presented. Furthermore, the syntheses and reactions of two new symmetrically substituted methane derivatives, containing either 1‐methylimidazole or 1‐methylbenzimidazole, are discussed. In this context, firstly, (1‐MeNCNC2H2)2CH2 and (1‐MeNCNC6H4)2CH2, and secondly, (NCSC6H4)CH2(NCOC6H4) and (NCSC6H4)CH2(1‐MeNCNC6H4), are used as parent compounds. They can be easily deprotonated at the central methylene bridge to generate a monoanionic structure akin to NacNac, so that the following complexes can be obtained: [Me2Al{(1‐MeNCNC2H2)2CH}], [Me2Al{(1‐MeNCNC6H4)2CH}], [Me2Al{(NCSC6H4)CH(NCOC6H4)}], [Me2Ga{(NCSC6H4)CH(NCOC6H4)}], [Me2Al{(NCSC6H4)CH(1‐MeNCNC6H4)}], [(THF)2Li{(1‐MeNCNC6H4)2CH}] and [(diox)2Li{(NCSC6H4)CH(1‐MeNCNC6H4)}]. These compounds have been fully characterised by single‐crystal X‐ray diffraction (in the solid state) and NMR spectroscopy (in solution).