Thorium(IV) alkyl synthesis from a thorium(III) cyclopentadienyl complex and an Nheterocyclic olefin
| Autor: | David P. Mills, Ashley J. Wooles, John A. Seed, Jingjing Liu, Stephen T. Liddle, Fabrizio Ortu, Alasdair Formanuik |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
Reaction mechanism
Inorganic chemistry chemistry.chemical_element Methyl 010402 general chemistry 01 natural sciences Biochemistry Medicinal chemistry thorium Inorganic Chemistry chemistry.chemical_compound N-heterocyclic olefin Cyclopentadienyl complex Materials Chemistry alkylidene Physical and Theoretical Chemistry Alkyl chemistry.chemical_classification Olefin fiber 010405 organic chemistry Organic Chemistry Thorium 0104 chemical sciences chemistry cyclopentadienyl Proton NMR Single crystal Derivative (chemistry) |
| Zdroj: | Liu, J, Seed, J, Formanuik, A, Ortu, F, Wooles, A, Mills, D & Liddle, S 2017, ' Thorium(IV) alkyl synthesis from a thorium(III) cyclopentadienyl complex and an Nheterocyclic olefin ', Journal of Organometallic Chemistry . https://doi.org/10.1016/j.jorganchem.2017.08.015 |
| DOI: | 10.1016/j.jorganchem.2017.08.015 |
| Popis: | Treatment of the tris(cyclopentadienyl) thorium(III) complex [Th(η5-Cp′′)3] [1, Cp′′ = C5H3-1,3-(SiMe3)2] with the N-heterocyclic olefin H2C=C(NMeCH)2 (2) reproducibly produces the thorium(IV)-methyl derivative [Th(η5-Cp′′)3(Me)] (3) along with MeImCH2CH2ImMe (Im = imidazole). The reaction mechanism, which is consistent with 1H NMR spectroscopic observations, is proposed to proceed via: (i) coordination of 2 to 1; (ii) one-electron transfer from thorium to 2; (iii) N-methyl cleavage and transfer to thorium to give 3; (iv) coupling of the resulting imidazolium radical by-product to give MeImCH2CH2ImMe. Complex 3 has been characterised by single crystal X-ray diffraction, multi-nuclear NMR and IR spectroscopies, and elemental analyses, and MeImCH2CH2ImMe by 1H NMR spectroscopy and mass spectrometry. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|