The complexes [MoCl3(1-N,2-Ph2P-C6H4)2] (1) and {MoCl(Nt-Bu)[1-micro(N),2-(Ph2P)C6H4]}2 (2) have been obtained from the reaction of 2-diphenylphosphinoaniline [1,2(NH2)(Ph2P)C6H4] with either sodium molybdate [Na2MoO4] (in the presence of Et3N and Me3SiCl) or [MoCl2(Nt-Bu)2(DME)]; the crystal structure of 1 reveals a novel MoNC2PN six-membered conjugated ring system derived from a P-N coupling reaction between two ligands, whilst that of 2 reveals bridging imido/terminal phosphine ligation.