Extending N-heterocyclic carbene ligands into the third dimension: a new type of hybrid phosphazane/NHC systemElectronic supplementary information (ESI) available: Methods and additional data. CCDC 10401231040125-1040128. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03966aDedicated to Professor Manfred Scheer on the occasion of his 60th birthday

A simple, "click" synthetic approach to a new type of hybrid phosph(III)azane/NHC system is described. The presence of the phosphazane P 2 N 2 ring unit, with P atoms flanking the NCN fragment and with this ring perpendicular to the binding site of the NHC, provides unique opportunities for modifying the electronic and steric character of these carbenes. A new type of hybrid phosph(III)azane/NHC system is described in which a phosphazane P 2 N 2 ring provides unique opportunities for modifying the electronic and steric character of these carbenes.