A Combined Experimental−Theoretical Study on the Lithiation/Electrophilic Quench Sequence of (η5-Cyclohexadienyl)Mn(CO)3 Complexes
| Autor: | Alina Chanaewa, Béatrice Jacques, Murielle Chavarot-Kerlidou, Françoise Rose-Munch, Hélène Gérard, Eric Rose |
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| Rok vydání: | 2008 |
| Předmět: | |
| Zdroj: | Organometallics. 27:626-636 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | An easy and versatile functionalization of (η5-cyclohexadienyl)Mn(CO)3 complexes by a lithiation/electrophilic quench sequence is described. Using TMSCl as a model electrophile, the reactivity of the series of substrates 1–5 was studied. In addition to the regiochemistry control by ortho-directing groups, such as OMe or Cl, the results suggest a strong influence of the Mn(CO)3 tripod conformation on the regioselectivity of the lithiation. In order to gain a better understanding of the reactivity features of the cyclohexadienyl ligand in the η5 complex, a theoretical investigation was undertaken. It indicates that the regioselectivity relies mainly on the intrinsic stabilities of the deprotonated intermediates, the species lithiated at C2, eclipsed by a Mn−CO bond, being the most stable one. The synthetic methodology was finally successfully extended to a representative range of electrophiles, giving access in good to excellent yields to η5 derivatives substituted by various heteroatoms (iodine, sulfur, or... |
| Databáze: | OpenAIRE |
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