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Reductive Elimination at Pb(II) Center of an (Amino)plumbylene-Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis |
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| Authors: | Vladislava Timofeeva José Miguel Léon Baeza Dr. Raphael Nougué Dr. Mikhail Syroeshkin Prof. Dr. Rene Segundo Rojas Guerrero Dr. Nathalie Saffon-Merceron Dr. Gül Altınbaş Özpınar Dr. Saskia Rathjen Prof. Dr. Thomas Müller Dr. Antoine Baceiredo Dr. Tsuyoshi Kato |
| Affiliation: | 1. Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse, France N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991 Moscow, Russia;2. Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse, France Departamento de Química Inorganica, Facultad de Química, Pontificia Universidad Catolica de Chile, Casilla 306, Santiago, 22 Chile;3. Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse, France;4. N. D. Zelinsky Institute of Organic Chemistry, Leninsky prosp. 47, 119991 Moscow, Russia;5. Departamento de Química Inorganica, Facultad de Química, Pontificia Universidad Catolica de Chile, Casilla 306, Santiago, 22 Chile;6. Institut de Chimie de Toulouse (FR 2599), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse, France;7. Institut für Chemie, Carl von Ossietzky Universität Oldenburg, Carl von Ossietzky-Strasse 9–11, 26111 Oldenburg, Germany |
| Abstract: | A stable (amino)plumbylene-substituted phosphaketene 3 was synthesized by the successive reactions of PbCl2 with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3 , at 80 °C, leads to the transient formation of corresponding amino- and phosphanylidene-phosphaketenes ( 6 and 7 ), via a reductive elimination at the PbII center forming new N−P and P−P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4 , which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access. |
| Keywords: | heterocycles phosphaketenes phosphanylidene phosphinidenes phosphoranes plumbylene |