The reaction of zerovalent nickel compounds with white phosphorus (P-4) is a barely explored route to binary nickel phosphide clusters. Here, we show that coordinatively and electronically unsaturated N-heterocyclic carbene (NHC) nickel(0) complexes afford unusual cluster compounds with P-1, P-3, P-5 and P-8 units. Using [Ni(IMes)(2)] [IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene], electron-deficient Ni3P4 and Ni3P6 clusters have been isolated, which can be described as superhypercloso and hypercloso clusters according to the Wade-Mingos rules. Use of the bulkier NHC complexes [Ni(IPr)(2)] or [(IPr)Ni(eta(6)-toluene)] [IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene] affords a closo-Ni3P8 cluster. Inverse-sandwich complexes [(NHC)(2)Ni2P5] (NHC=IMes, IPr) with an aromatic cyclo-P-5(-) ligand were identified as additional products.