Organometallic chemistry of Ga⁺: Formation of an unusual gallium dimer in the coordination sphere of ruthenium

Abstract:

New insights into the distinct organometallic chemistry of the Ga + ion are presented. Ga+ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH2) 32-) attached at Ru by insertion into a Ru-C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)3- [η3-(CH2)2C{CH2(μ-Ga)}]} 2][(BArF)2] (4) (Cp* = C 5Me5, [BArF] = [B{C6H 3-(CF3)2}4]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga+ as a ligand was found in the compound [Ru(PCy3)2(GaCp*)2(Ga)][BAr F] (6) (Cy = C6H11, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga+ represents a pure σ/π-accepting ligand in this case. © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

Año de publicación:

2008

Keywords:

• metal-metal interactions
• ruthenium
• Density functional calculations
• Low-valent ion
• Gallium

Fuente:

google

scopus