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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
Author(s) -
Brandl Martin,
Ebner Alexander,
Kubicki Marek M.,
Mugnier Yves,
Wachter Joachim,
VigierJuteau Estelle,
Zabel Manfred
Publication year - 2007
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600690
Subject(s) - chemistry , crystallography , block (permutation group theory) , electrochemistry , tetragonal crystal system , tetrahedron , redox , density functional theory , crystal structure , computational chemistry , electrode , inorganic chemistry , combinatorics , mathematics
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′ = t BuC 5 H 4 ) is used under similar conditions dark‐brown [(Cp′Nb) 2 Ni 5 Te 7 (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 Te 5 tetragonal pyramids stacked into each other in an opposite way. Six of the Te bridges form two triangular faces, each of which is capped by a Cp′Nb fragment. Additionally, two dppm ligands bridge the long Ni–Ni edges of the Ni 4 bases. Oxidation of 3 with [(C 5 H 5 ) 2 Fe]BPh 4 gives paramagnetic [(Cp* 2 Nb) 2 NiTe 4 ]BPh 4 ( 6 ), whereas oxidation with [(C 5 H 5 ) 2 Fe]PF 6 proceeds with fluoride transfer to give [Cp* 2 NbF 2 ]PF 6 ( 5 ). Electrochemical studies of 3 reveal the existence of the redox couples [ 3 ] 2+ /[ 3 ] + /[ 3 ] 0 /[ 3 ] – /[ 3 ] 2– . Density functional calculations carried out on the different oxidation states of 3 reveal the following main features: the persistent presence of Nb–Ni bonds and the retention of Te–Te bonds in cationic and neutral species and their breaking off in reduced forms. Irrespective of the initial site of electrochemical attack, the Te atoms and Cp rings are principally affected in the final products.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)