NHCs as Neutral Donors towards Polyphosphorus Complexes |
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| Authors: | Dr Felix Riedlberger Dr Stefano Todisco Prof?Dr Piero Mastrorilli Prof?Dr Alexey Y Timoshkin Dr Michael Seidl Prof?Dr Manfred Scheer |
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| Institution: | 1. Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany;2. Dipartimento di Ingeneria Civile, Ambientale, del Territorito Edile e di Chimica (DICATECh), Politecnico di Bari, Via Orabona 4, 70125 Bari, Italy;3. Institute of Chemistry, St. Petersburg State University, Universitetskaya nab. 7/9, 199034 St. Petersburg, Russia |
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| Abstract: | The first adducts of NHCs (=N-heterocyclic carbenes) with aromatic polyphosphorus complexes are reported. The reactions of Cp*Fe(η5-P5)] ( 1 ) (Cp*=pentamethyl-cyclopentadienyl) with IMe (=1,3,4,5-tetramethylimidazolin-2-ylidene), IMes (=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene) and IDipp (=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) led to the corresponding neutral adducts which can be isolated in the solid state. However, in solution, they quickly undergo a dissociative equilibrium between the adduct and 1 including the corresponding NHC. The equilibrium is influenced by the bulkiness of the NHC. Cp′′Ta(CO)2(η4-P4)] (Cp′′=1,3-di-tert-butylcyclopentadienyl) reacts with IMe under P atom abstraction to give an unprecedented cyclo-P3-containing anionic tantalum complex. DFT calculations shed light onto the energetics of the reaction pathways. |
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| Keywords: | iron N-heterocyclic carbenes NMR spectroscopy nucleophilic attack phosphorus tantalum |
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