[Ni 8 (μ 4 ‐PPh) 6 (PPh 3 ) 4 ] and [Ni 9 (μ 4 ‐PPh) 6 (PPh 3 ) 4 ]; Cluster with Coordinatively Unsaturated Ni‐Atoms

The novel nickel‐phosphane clusters 1 and 2 have almost identical structures: In 1 the Ni atoms form a distorted cube, each face of which is roofed by a PPh ligand. The PPh 3 ligands are alternatingly bound to Ni such that a coordination gap remains at four of the Ni atoms. In 2 one of the gaps is occupied by a Ni atom.— 1 is formed from NiCl 2 , PPh 3 , and PhP(SiMe 3 ) 2 under specific conditions or by reduction of 3 with Na/Hg; 2 is obtained by the same reduction, but in the presence of NiCl 2 .