Functionally Altered Ruthenaindenes with Electron-Rich and Electron-Poor Substituents
作者:Hsiu L. Li、Synøve Ø. Scottwell、James D. Watson、Timothy E. Elton、Hon C. Yu、Mohan Bhadbhade、Leslie D. Field
DOI:10.1021/acs.organomet.9b00788
日期:2020.2.10
groups on the aromatic ring have significantly lower oxidation potentials in comparison to complexes with electron-withdrawing groups. Even though the substitution of the aromatic ring with electron-donating/-withdrawing groups is remote from the metal center, the electronic properties of the substituents are relayed effectively to the metal center, indicating that the metal center in the ruthenaindenes
Reaction of ruthenium bis-acetylide complexes with 2,6-lutidinium tetrafluoroborate gave butenynyl complexes cis-[Ru(eta(3)-RC CC=C(H)R)(PMe(3))(4)]BF(4) in moderate to good yields. The structure of cis[Ru(eta(3)-tBuC CC=C(H)tBu)(PMe(3))(4)]BF(4) was determined crystallographically. Attempts to prepare cis[Ru(eta(3)-MeC CC=C(H)Me)(PMe(3))(4)]BF(4) resulted in the formation of two isomers, which differ in the stereochemistry about the double bond. The reaction of two bis-acetylide complexes with methyl triflate afforded butenynyl-type complexes cis- [Ru(eta(3)-RC CC=C(Me)R)(PMe(3))(4)](+) (R = Me, Ph). The mixed acetylide-vinylidene complex trans-[Ru(C CSiMe(3))(C=CH(2))(PMe(3))(4)]PF(6) was prepared by the reaction of trans-Ru(C CSiMe(3))(2)(PMe(3))(4) with ammonium hexafluorophosphate. In addition, the crystal structure of trans-[Ru(C CH)(C=CH(2))(PMe(3))(4)]BF(4) is reported.