An unusual NiSiP cluster formed by complexation and thermolysis

[LSi(η 2 -P 4 )] (L = CH[C(Me)N(Dipp)][C(CH 2 )N(Dipp)], Dipp = 2,6-diisopropylphenyl) forms well-defined 1 : 1 and 2 : 1 complexes with N-heterocyclic carbene nickel fragments. The cluster compound [(IDipp)Ni 2 P 8 (SiL) 2 ] (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) is selectively formed by thermolysis of the complex [(IDipp)Ni(μ-η 2:2 -P 4 )SiL]. A ternary Ni 2 Si 2 P 8 cluster compound is formed selectively by thermolysis of a well-defined nickel complex. This reaction illustrates a potentially useful strategy for the preparation of heteroatom-doped transition metal-phosphide clusters.