Negishi's Reagent Versus Rosenthal's Reagent in the Formation of Zirconacyclopentadienes |
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| Authors: | Sara Urrego-Riveros Isabel-Maria Ramirez y Medina Daniel Duvinage Dr Enno Lork Frank D Sönnichsen Prof Dr Anne Staubitz |
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| Institution: | 1. Institute for Organic and Analytical Chemistry/MAPEX Center for, Materials and Processes, University of Bremen, Leobener Str. 7/ Bibliothekstr. 1, 28359 Bremen, Germany;2. Institute for Inorganic Chemistry and Crystallography/, MAPEX Center for Materials and Processes, University of Bremen, Leobener Str. 7/Bibliothekstr. 1, 28359 Bremen, Germany;3. Otto-Diels-Institute for Organic Chemistry, University of Kiel, Otto-Hahn-Platz 4, 24098 Kiel, Germany |
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| Abstract: | Zirconacyclopentadienes are versatile precursors for a large number of heteroles, which are accessible by Zr-element exchange reactions. The vast majority of reports describe their preparation by the use of Negishi′s reagent, which is a species that is formed in situ. The zirconacyclopentadiene is then formed by the addition of one equivalent of a diyne or two equivalents of a monoyne moiety to this Negishi species. Another route involves Rosenthal′s reagent (Cp2Zr(py)Me3SiC≡CSiMe3), which then reacts with a diyne or monoyne moiety. In this work, the efficiency of both routes was compared in terms of reaction time, stability of the product in the reaction mixture, and yield. The synthetic implications of using both routes are evaluated. Novel zirconacyclopentadienes were synthesized, characterized directly from the reaction mixture, and crystal structures could be obtained in most cases. |
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| Keywords: | metallacycles Negishi′s reagent Rosenthal′s reagent substituent effects zirconium |
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