Design of Self‐Adapting N‐Heteroaromatic Substituted Claw Ligands as E−/M+(E = P‐Block Element, M = Main‐Group Metal) Charge Spacers

Monoanionic bi‐ and tridentate ligand systems emulating the structural features of the well‐known poly(pyrazolyl)borates are created by bridging heteroaromatic rings with formally negatively charged p‐block elements. Their properties and versatility are exemplified by their complexes with main group metals. Due to their N(σ)‐donating and π‐interacting ability, as well as the flexibility of the substituent bonding, these ligand systems have the potential to adapt both geometrically and electronically to the coordination requirements of the complexed metal. Within these complexes, the heteroaromatic substituents operate as charge spacers between the formally anionic center and the metal cation without encapsulating either site. This provides possible applications in the creation of reactive soft/hard bimetallic reagents, the realization of multinuclear arrays, and the design of preorganized CVD precursors, particularly en route to III/V‐semiconducting thin films.