Formation of Ruthenaindenes by Cyclometalation of Ruthenium(II) Diarylbutenyne Complexes
摘要:
The reaction of diarylbutenynylruthenium complexes [Ru(eta(3)-C CC(6)H(4)R)=C(R')C(6)H(4)R)-(PMe(3))(4)](+) (C(6)H(4)R = C(6)H(4)R = C(6)H(4)-4-'Bu, Ph, C(6)H(4)-4-Me; R' = H, Me) with dimethylinagnesium yields the cyclometalated ruthenaidene complexes [Ru(C(C CC(6)H(4)R)=C(R')'C(6)H(3)R)(PMe(3))(4)] with ruthenium incorporated into the five-membered ring of an indene. The reaction involves the initial formation of methylruthenium complexes, which then rearrange with the elimination of methane to yield the product, The complexes [Ru(C(C CC(6)H(4)R)=C(R')C(6)H(3)R)(PMe(3))(4)] (C(6)H(4)R = C(6)H(4)-4-'Bu, R' = H; C(6)H(4)R = Ph, R' = Me) were crystallographically characterized.
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