0000000000805682
AUTHOR
Martin Brandl
Synthesis, reactivity and structures of ruthenium carbonyl clusters with telluride and hydride ligands
The reaction of [Cp* 2 Nb(Te 2 H)] ( 1 ) (Cp*=C 5 Me 5 ) with [Ru 3 (CO) 12 ] in boiling toluene gave [Ru 3 (μ 2 -H) 2 (CO) 9 (μ 3 -Te)] ( 2 ), [Ru 6 (μ 3 -H)(CO) 15 (μ 3 -Te) 3 ][Cp* 2 Nb(CO) 2 ] ( 3 ) and [Ru 5 (μ 2 -H)(CO) 14 (μ 4 -Te)][Cp* 2 Nb(CO) 2 ] ( 4 ) along with already known [Ru 4 (CO) 11 (μ 4 -Te) 2 ] ( 5 ). Complexes 2 – 4 were analytically and spectroscopically characterized and X-ray diffraction analyses of 3 and 4 were carried out. The anion of 3 is built up of a triangular hexametallic core of C 3 v symmetry, in which the central Ru 3 triangle, being bridged by a μ 3 -H ligand, is composed of three corner-linked Ru 3 Te tetrahedra. The main structural feature of the anion …
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…