Brandl, Martin and Ebner, Alexander and Kubicki, Marek M. and Mugnier, Yves and Wachter, Joachim and Vigier-Juteau, Estelle and Zabel, Manfred (2007) Syntheses, properties and structures of [{(C5Me5)(2)Nb}(2)NiTe4] and [(tBuC(5)H(4)Nb)(2)Ni5Te7(Ph2PCH2PPh2)(2): The quest for tetratelluronickelate clusters. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY (7). pp. 994-1003. ISSN 1434-1948,
Full text not available from this repository.Abstract
The reaction of [Ni(COD)(2)] with [CP*2NbTe2H] (1; Cp* = eta-C5Me5) in the presence of Ph2PCH2PPh2 (dppm) in boiling toluene gives black-violet [(CP*Nb-2)(2)NiTe4] (3). If [CP'2NbTe2H] (2; Cp' = tBuC(5)H(4)) is used under similar conditions dark-brown [(Cp'Nb)(2)Ni5Te7(dpPM)(2)] (4) is formed. The structures of 3 and 4 have been determined crystallographically. Complex 3 contains a severely distorted NiTe4 tetrahedron to which two mobocene groups are coordinated. Density functional analysis of the electronic structure of the NiTe4 building block shows that it is best described as an [Ni(eta(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 [(C5H5)(2)Fe]BPh4 gives paramagnetic [(CP*Nb-2)(2)NiTe4]BPh4 (6), whereas oxidation with [(C5H5)(2)FejPF(6) proceeds with fluoride transfer to give lcp*2NbF2]PF, (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. (c) Wiley-VCH Verlag GmbH & Co. KGaA.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | NICKEL CARBONYL CLUSTERS; TRANSITION-METAL; CRYSTAL-STRUCTURES; ICOSAHEDRAL CAGES; NIOBOCENE LIGANDS; BONDING ANALYSIS; COMPLEXES; DIANIONS; SE; ANION; niobium; nickel; tellurium; electrochemistry; density functional calculations |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Arbeitskreis Dr. Joachim Wachter |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 21 Dec 2020 13:24 |
| Last Modified: | 21 Dec 2020 13:24 |
| URI: | https://pred.uni-regensburg.de/id/eprint/33071 |
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