Brunner, Henri and Lucas, Dominique and Monzon, Teresa and Mugnier, Yves and Nuber, Bernhard and Stubenhofer, Bernhard and Stückl, A. Claudia and Wachter, Joachim and Wanninger, Robert and Zabel, Manfred (2000) Metal telluride clusters composed of niobocene carbonyl, telluride, and cobalt carbonyl units: Syntheses, structures, and reactivity. CHEMISTRY-A EUROPEAN JOURNAL, 6 (3). pp. 493-503. ISSN 0947-6539
Full text not available from this repository.Abstract
The reaction of [(Cp2NbTe2H)-Nb-#] (1(#); Cp-# = Cp* (C5Me5) or Cp-x (C5Me4Et)) with two equivalents of [Co-2(CO)(8)] gives a series of cobalt carbonyl telluride clusters that contain different types of niobocene carbonyl fragments. At 0 degrees C, [(Cp2NbTe2Co3)-Nb-#(CO)(7)] (2(#)) and [Co4Te2(CO)(10)] (3) are formed which disappear at higher temperatures: in boiling toluene a mixture of [cat(2)][Co9Te6(CO)(8)] (5(#)) (cat = [(Cp2Nb)-Nb-#(CO)(2)](+)) and [cat(2)][Co11Te7(CO)(10)] (6(#)) is formed along with [cat][Co(CO)(4)] (4(#)). Complexes 6(#) transform into [cat][Co11Te7(CO)(10)] (7(#)) upon interaction with HPF6 or wet SiO2. The molecular structures of 2(Cp-x), 4(Cp-x), 5(Cp*), 6(Cp*) and 7(Cp*) have been determined by X-ray crystallography. The structure of the neutral 2(Cp-x) consists of a [Co-3(CO)(6)Te-2] bipyramid which is connected to a [(C5Me4Et)(2)Nb(CO)] fragment through a mu(4)-Te bridge. The ionic structures of 4(Cp-x), 5(Cp*), 6(Cp*) and 7(Cp*) each contain one (4, 7) or two (5, 6) [(Cp2Nb)-Nb-#(CO)(2)](+) cations. Apart from 4, the anionic counterparts each contain an interstitial Co atom and are hexacapped cubic cluster anions [Co9Te6(CO)(8)](2-) (5) or heptacapped pentagonal prismatic cluster anions [Co11Te7(CO)(10)](n-) (n = 2: [6](2-), n = 1: [7](-)), respectively. Electrochemical studies established a reversible electron transfer between the anionic clusters [Co11Te7(CO)(10)](-) and [Co11Te7(CO)(10)](2-) in 6# and 7# and provided evidence for the existence of species containing [Co11Te7(CO)(10)] and [Co11Te7(CO)(10)](3-). The electronic structures of the new clusters and their relative stabilities are examined by means of DFT calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | BONDING ANALYSIS; CUBIC CLUSTERS; ORGANOMETALLIC COMPOUNDS; MOLECULAR-STRUCTURES; TRANSITION; COMPLEXES; APPROXIMATION; COORDINATION; LIGANDS; CS3TE22; carbonyl complexes; cluster compounds; cobalt; niobium; tellurium |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Arbeitskreis Dr. Joachim Wachter Chemistry and Pharmacy > Institut für Anorganische Chemie > Alumni or Retired Professors > Prof. Dr. Henri Brunner |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 01 Jun 2022 06:07 |
| Last Modified: | 01 Jun 2022 06:07 |
| URI: | https://pred.uni-regensburg.de/id/eprint/42830 |
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