Synthesis, crystal structure and quantum chemical investigation of the phosphine-stabilized Ni-S-cluster [Ni32S24(PPh3)10]

The reaction of PrSSiMe3 and S(SiMe3)(2) with [NiCl2(PPh3)(2)] in THF results in crystals of [Ni32S24(PPh3)(10)]center dot 6THF (1). The structure of this compound was determined by single crystal X-ray structural analysis. Since the crystallographic analysis for [Ni32S24(PPh3)(10)] remained ambiguous with respect of the assignment of the disordered Ni- and S-atoms in the centre of the cluster, we performed DFT computations to address this problem. The theoretical investigations support the composition of the new sulfur-bridged nickel cluster compound [Ni32S24(PPh3)(10)]. We report herein the synthesis, structure and theoretical investigation of [Ni32S24(PPh3)(10)]. In addition we comment on the analogous selenium compound.