The Coordination Chemistry of the N‐Donor‐Substituted Phosphazanes.

Phosph(III)azanes, featuring the heterocyclobutane P2N2 ring, have now been established as building blocks in main‐group coordination and supramolecular compounds. Previous studies have largely involved their use as neutral P‐donor ligands or as anionic N‐donor ligands, derived from deprotonation of amido‐phosphazanes [RNHP(μ‐NR)]2. The use of neutral amido‐phosphazanes themselves as chelating, H‐bond donors in anion receptors has also been an area of recent interest because of the ease by which the proton acidity and anion binding constants can be modulated, by the incorporation of electron‐withdrawing exo‐ and endo‐cyclic groups (R) and by the coordination of transition metals to the ring P atoms. We observed recently that the effect of P,N‐chelation of metal atoms to the P atoms of cis‐[(2‐py)NHP(μ‐NtBu)]2 (2‐py=2‐pyridyl) not only pre‐organises the N−H functionality for optimum H‐bonding to anions but also results in a large increase in anion binding constants, well above those for traditional organic receptors like squaramides and ureas. Here, we report a broader investigation of ligand chemistry of [(2‐py)NHP(μ‐tNBu)]2 (and of the new quinolyl derivative [(8‐Qu)NHP(μ‐NtBu)]2 (8‐Qu=8‐quinolyl). The additional N‐donor functionality of the heterocyclic substituents and its position has a marked effect on the anion and metal coordination chemistry of both species, leading to novel structural behaviour and reactivity compared to unfunctionalized counterparts. [ABSTRACT FROM AUTHOR]