Bis(η-tert-butylcyclopentadienyl)hydridoniobium Ditelluride, a Convenient Reagent for the Synthesis of Polynuclear Metal Telluride Complexes
2002; Wiley; Volume: 2002; Issue: 6 Linguagem: Inglês
10.1002/1099-0682(200206)2002
ISSN1099-0682
AutoresHenri Brunner, Hélène Cattey, David Evrard, Marek M. Kubicki, Yves Mugnier, E. Vigier, Joachim Wächter, R. Wanninger, Manfred Zabel,
Tópico(s)Synthesis and characterization of novel inorganic/organometallic compounds
ResumoEuropean Journal of Inorganic ChemistryVolume 2002, Issue 6 p. 1315-1325 Full Paper Bis(η-tert-butylcyclopentadienyl)hydridoniobium Ditelluride, a Convenient Reagent for the Synthesis of Polynuclear Metal Telluride Complexes Henri Brunner, Henri Brunner Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this authorHelene Cattey, Helene Cattey Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorDavid Evrard, David Evrard Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorMarek M. Kubicki, Marek M. Kubicki Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorYves Mugnier, Yves Mugnier Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorEstelle Vigier, Estelle Vigier Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorJoachim Wachter, Joachim Wachter Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this authorRobert Wanninger, Robert Wanninger Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this authorManfred Zabel, Manfred Zabel Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this author Henri Brunner, Henri Brunner Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this authorHelene Cattey, Helene Cattey Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorDavid Evrard, David Evrard Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorMarek M. Kubicki, Marek M. Kubicki Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorYves Mugnier, Yves Mugnier Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorEstelle Vigier, Estelle Vigier Laboratoire de Synthèse et d’Electrosynthèse Organométalliques (UMR 5632), Université de Bourgogne, 21100 Dijon, FranceSearch for more papers by this authorJoachim Wachter, Joachim Wachter Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this authorRobert Wanninger, Robert Wanninger Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this authorManfred Zabel, Manfred Zabel Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, GermanySearch for more papers by this author First published: 24 April 2002 https://doi.org/10.1002/1099-0682(200206)2002:6 3.0.CO;2-0Citations: 13Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Abstract Reaction of [Cp′2NbH3] (Cp′ = tBuC5H4) with Te powder in THF gives [Cp′2Nb(Te2)H] (1) and [Cp′6Nb4Te4O] (2). The yield of 1 varies between 10 and 81% depending on the degree of oxygen contamination of the reagents. Complexes 1 and 2 react with [Cr(CO)5THF] to give [Cp′2Nb(Te2)H·Cr(CO)5] (3) and [Cp′6Nb4Te4O·2Cr(CO)5] (4), respectively. The crystal structures of 2−4 have been determined. In 3 a Te2 unit and an H ligand are coordinated to a bent niobocene moiety; the Cr(CO)5 group is attached to the lateral Te atom. The molecular cores of 2 and 4 are practically identical in that they contain two planar Nb2Te2 rings connected by a nearly linear oxygen bridge. Each of the “outer” Nb atoms bears two Cp′ ligands, whereas the “inner” Nb atom only has one such ligand. An additional structural feature in 4 is two Cr(CO)5 groups, attached to one Te bridge of each Nb2Te2 ring. Thermolysis of 3 leads to the formation of diamagnetic [Cp′4Nb2Te2] (5), which also contains a planar Nb2Te2 core. The relatively long transannular Nb−Nb distance (3.647 Å) is consistent, according to DFT calculations, with a through-space Nb−Nb coupling. Complex 5 reacts with CH3I with successive methylation of both Te bridges to give [Cp′4Nb2Te(CH3Te)]I ([6]I) and [Cp′4Nb2(CH3Te)2]I2 ([7]I2). The crystal structure of [7]I2 may be derived from that of 5, the incoming CH3 groups being fixed at the Te bridges in a trans position. 1H NMR spectroscopic investigations reveal a restricted rotation around the Cp′−Nb bonds in 2 and 5 at −90 °C and in 4 and [7]I2 at ambient temperature. Electrochemical studies have been carried out on 5, [6]I, and [7]I2, showing that all compounds undergo two reversible one-electron reduction steps. The reduction potential decreases by ca. 1.6 V when going from 5 to [7]I2. There is also a clear linear correlation between the reduction potentials measured for 5 to [7]I2 and the energies of the corresponding LUMO’s calculated at the DFT/B3LYP level. These LUMO’s bear some 70% contribution from both Nb atoms and, consequently, the reduction processes mainly operate at both metallic centers. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002) References 1 J. M. Fischer , W. E. Piers , L. R. MacGillivray , M. J. Zaworotko , Inorg. Chem. 1994 , 34 , 2499 −2500 . 10.1021/ic00114a005 Web of Science®Google Scholar 2a G. Tainturier , M. Fahim , B. Gautheron , J. Organomet. Chem. 1989 , 373 , 193 −202 . 10.1016/0022-328X(89)85045-4 CASWeb of Science®Google Scholar 2b G. Tainturier , M. Fahim , G. Trouvé-Bellan , B. Gautheron , J. Organomet. Chem. 1989 , 376 , 321 −332 . 10.1016/0022-328X(89)85142-3 CASWeb of Science®Google Scholar 3 3a W. A. Howard , G. Parkin , A. L. 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