Syntheses, Properties and Structures of [{(C 5 Me 5 ) 2 Nb} 2 NiTe 4 ] and [( t BuC 5 H 4 Nb) 2 Ni 5 Te 7 (Ph 2 PCH 2 PPh 2 ) 2 ]: The Quest for Tetratelluronickelate Clusters

The reaction of [Ni(COD) 2 ] with [Cp* 2 NbTe 2 H] (1; Cp * = η-C 5 Me 5 ) in the presence of Ph 2 PCH 2 PPh 2 (dppm) in boiling toluene gives black-violet [(Cp * 2 Nb) 2 NiTe 4 ] (3). If [Cp' 2 NbTe 2 H] (2; Cp' = tBuC 5 H 4 ) is used under similar conditions dark-brown [(Cp'Nb)2Ni5Te7(dppm)2] (4) is formed. The structures of 3 and 4 have been determined crystallographically. Complex 3 contains a severely distorted NiTe 4 tetrahedron to which two niobocene groups are coordinated. Density functional analysis of the electronic structure of the NiTe 4 building block shows that it is best described as an [Ni(η 2 -Te 2 ) 2 ] 2- fragment. The structure of 4 reveals the presence of two Ni 5 and T…