Abstract
The title complex was prepared m 87% yield from the deprotonation of [Ru(C6Me6)2](BF4)2 with excess potassium tert-butoxide in THF at −78 °C. Treatment of the mixed-sandwhich complex [Ru(1,2-C6H4Me2)(C6Me6)](PF6)2 with excess potassium tert-butoxide resulted in preferential deprotonation of the hexamethylbenzene ligand, giving o-xylylene complex Ru(η6-1,2-C6H4Me2)[η4-C6Me4(CH2)2]. Attempts to prepare o-xylylene complexes bearing no ring methyl groups by deprotonation of [Ru(o-xylene)2]2+ or [Ru(benzene) (o-xylene)2]2+ failed to give isolable complexes. The cyclohexadienyl complex [Ru(η6-C6Me6) (η5-C6Me5CH2)]+ was prepared as the PF6-, BPh4-, or CF3SO3- salt by monodeprotonating [Ru-(C6Me6)2](PF6)2 with 1 equiv of potassium tert-butoxide, by treating the title complex with 1 equiv of trifluoromethanesulfonic acid, or by stirring an equimolar mixture of [Ru(C6Me6)2](BF4)2 and the title complex in acetonitrile. The exomethylene carbons of the coordinated o-xylylene were alkylated with excess CF3SO3Me to give [Ru(C6Me6)(1,2-C6Me4Et2)]2+ or were hydrogenated under catalytic conditions to give the single or doubly hydrogenated complexes Ru(η4-C6HMe5CH2)(η6-C6Me6) and Ru(η4-5,6-C6Me6H2) (η6-C6Me6). The singly hydrogenated product is a tautomer of the known 18-electron complex Ru(C6Me6)2 but is much more stable toward oxidation. Treatment with Fe(CO)4(NMe3) gave a product bearing an Fe(CO)3 group coordinated to the exomethylene diene system, along with an unexpected product characterized as a complex in which an iron acylate strap connects the two dissimilar hexamethylbenzene ligands. The coordinated o-xylylene ligand failed to undergo cycloaddition reactions when treated with dienophiles.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 3117-3121 |
| Number of pages | 5 |
| Journal | Organometallics |
| Volume | 11 |
| Issue number | 9 |
| DOIs | |
| State | Published - Sep 1 1992 |