The availability of the phosphorus lone pair highlights the potential application of azophosphines as ligands. The P-N=N functionality classifies azophosphines as 1,3-P,N ligands. 1,3-P,N ligands display diverse coordination modes, including κ 1 N, κ 1 P, κ 2 P,N, and μP,N, and have applications in (cooperative) catalysis, bioinorganic chemistry and photoluminescence. All previous examples of 1,3-P,N ligands feature C as the central element. However, control of the target coordination mode during synthesis, and subsequent isolation of the product, can be challenging. We hypothesised the central nitrogen of azophosphines would reduce charge density at the terminal nitrogen and enable finer control of coordination mode.