Abstract
Deprotonation of cationic pentamethylcyclopentadienyl dppp ruthenium vinylidene complexes containing electron-withdrawing groups at the vinylidene ligand yielded cyclopropenyl complexes ([Ru] = (η5-C5Me5)(dppp)Ru, dppp = Ph2PCH2CH2CH2PPh2, R = CN, 3a; R = CO2CH3, 3b). Insertion of acetone into the three-membered ring of 3a gave the neutral dihydrofuranyl complex [Ru]-CC(Ph)CH(CN)CMe2O (4). Electrophilic addition at Cβ of 4 afforded cationic carbene complexes (R‘ = CH2CN, 5a; R‘ = CH2CO2CH3, 5b; R‘ = H, 7; R‘ = HgCl, 8). Complexes 5a and 5b transformed to (6) by elimination of small organic molecules. Reactivity of ruthenium complexes with a C5Me5 ligand is different from those with a C5H5 ligand and could be ascribed to electronic and steric effects. Reaction of [Ru]N3 with ICH2CN gave [Ru]NCH2I (11). Crystal structures of complexes 3a, 4, 6, 7, and 11 are also reported.
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