625129-66-0Relevant academic research and scientific papers
Diastereoselective Hydride Addition to [Tp′W(CO)(PhCCMe)(NH=CRR′)][BAr′4]: Effects of Equilibrium and Kinetic Acidity
Vogeley, Neil J.,White, Peter S.,Templeton, Joseph L.
, p. 1378 - 1389 (2008/10/09)
A series of alkyl and aryl amido, imine, azavinylidene, and amine complexes containing the [Tp′W(CO)(PhCCMe)]+ fragment have been synthesized. Reaction of Na[HBEt3] with an E/Z mixture of [Tp′W(CO)(PhCCMe)(NH=CMeEt)] [BAr′4] results in hydride addition at the imine carbon to form the amido complex with high diastereoselectivity. This high diastereoselectivity reflects differentiation between methyl and ethyl groups on the substrate imine carbon. A competing reaction forms an azavinylidene complex as a minor product via deprotonation of the coordinated imine ligand in the reagent. The ratio of amido to azavinylidene products tracks the E to Z isomer ratio and suggests that different reaction pathways characterize these two isomers. Relative pKa's of the various imine and amine complexes have been measured in THF, and kinetic acidity measurements of related imine complexes have been used to help understand these results.
