In this work we broaden the scope of azophosphines by systematically varying the electronic properties of the N-aryl substituent and explore how this affects their structural and spectroscopic characteristics. The azophosphine-selenides are synthesised to probe how these electronic variations affect the Pdonor properties of the azophosphines. The azophosphines are subsequently assessed as ligands in ruthenium piano stool complexes. Finally, we demonstrate that these Ru complexes are catalytically active in the transfer hydrogenation of acetophenone without the need for a strong base additive.