The reaction of two equivalents of (TMEDA)Li[(EP(i)Pr(2))(TeP(i)Pr(2))N] (E = S, Se) with NiBr(2)(DME) in THF at 23 degrees C yields homoleptic complexes of heterodichalcogenido PNP ligands Ni[(EP(i)Pr(2))(TeP(i)Pr(2))N](2) (2, E = S; 3, E = Se). Similarly, the complexes Ni[(P(i)Pr(2))(EP(i)Pr(2))N](2) (4, E = Se; 5, E = Te) are obtained by in situ deprotonation of the neutral monochalcogenides E=P(i)Pr(2)NP(H)(i)Pr(2) (E = Se, Te) with (n)BuLi in THF at -78 degrees C followed by addition of NiBr(2)(DME). The complexes 2-5 have been characterised by multinuclear ((1)H, (31)P, (77)Se and (125)Te) NMR spectroscopy in solution and by X-ray crystallography in the solid state, the results of which show that they all exist as the square planar, trans isomers. Aerosol-assisted chemical vapour deposition (AACVD) of Ni[(SeP(i)Pr(2))(TeP(i)Pr(2))N](2) yields crystalline Ni(0.51)Te films at 450-500 degrees C, which were analysed by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS).