期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 26, 期 69, 页码 16251-16255出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202003393
关键词
iron; N-heterocyclic carbenes; NMR spectroscopy; nucleophilic attack; phosphorus; tantalum
资金
- Deutsche Forschungsgemeinschaft (DFG) [Sche 384/38-1]
The first adducts of NHCs (=N-heterocyclic carbenes) with aromatic polyphosphorus complexes are reported. The reactions of [Cp*Fe(eta(5)-P-5)] (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)(eta(4)-P-4)] (Cp ''=1,3-di-tert-butylcyclopentadienyl) reacts with IMe under P atom abstraction to give an unprecedented cyclo-P-3-containing anionic tantalum complex. DFT calculations shed light onto the energetics of the reaction pathways.
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