Coordination chemistry of dialkylcyanamides: Binding properties, synthesis of metal complexes, and ligand reactivity

•Coordination modes and synthetic routes to dialkylcyanamide (NCNAlk2) complexes are reviewed.•Structural features, properties, and reactivity modes of NCNAlk2 ligands are systemized.•In many instances metal-bound NCNAlk2exhibit different behavior to conventional NCR nitriles.

Activation of conventional NCR nitriles (R = Alk, Ar) by their ligation to metal centers has been intensively studied in recent decades. By contrast, the chemistry of dialkylcyanamides (NCNAlk2) has been comparably less investigated. Reports on the coordination chemistry of these species indicate that in many instances NCNAlk2 molecules exhibit excitingly different behaviors – at both quantitative and qualitative levels – compared with NCR ligands. This review considers the coordination chemistry of dialkylcyanamides with a particular emphasis on comparison to conventional nitriles. An overview of the coordination modes of NCNAlk2 ligands and synthetic routes to dialkylcyanamide complexes (reported to date) are presented. The structural features and properties of these complexes are discussed, and the reactivity modes of dialkylcyanamide ligands are systemized.