sigma or pi? Bonding interactions in a series of rhenium metallotetrylenes
Résumé
Salt metathesis reactions between a low-valent rhenium(I) complex, Na[Re(eta(5)-Cp)(BDI)] (BDI = N,N'-bis (2,6-diisopropylphenyl)-3,5-dimethyl-beta-diketiminate), and a series of amidinate-supported tetrylenes of the form ECI[PhC((NBu)-Bu-t)(2)]) (E = Si, Ge, Sn) led to rhenium metallotetrylenes Re(E[PhC((NBu)-Bu-t)(2)])(eta(5)-Cp)(BDI) (E = Si (1a), Ge (2), Sn (4)) with varying extents of Re-E multiple bonding. Whereas the rhenium-stannylene 4 adopts a sigma-metallotetrylene arrangement featuring a Re E single bond, the rhenium-silylene (1a) and -germylene (2) both engage in pi-interactions to form short Re-E multiple bonds. Temperature was found to play a crucial role in reactions between Na(Re(eta(5)-Cp)(BDI)] and SiCl[PhC((NBu)-Bu-t)(2)], as manipulation of reaction conditions led to isolation of an unusual rhenium-silane, (BDI)Re(mu-eta(5).eta(1)-C5H4)(SiH[PhC((NBu)-Bu-t)(2)]) (1b) and a dinitrogen bridged rhenium-silylene, (eta(5)-Cp)(BDI)Re(mu-N-2)Si(PhC((NBu)-Bu-t)(2)] (1c), in addition to la. Finally, the reaction of Na(Re(eta(5)-Cp)(BDI)] with GeCl2 center dot dioxane led to a rare mu(2)-tetrelido complex, mu(2)-Ge(Re(eta(5)-Cp)(BDI)](2) (3). Bonding interactions within these complexes are discussed through the lens of various spectroscopic, structural, and computational investigations.
Domaines
| Origine | Fichiers produits par l'(les) auteur(s) |
|---|---|
| Licence |