om020913x_si_001.pdf (316.56 kB)

Synthesis of Dinuclear and Trinuclear Ruthenium Cyclopropenyl Complexes

Download (316.56 kB)
journal contribution
posted on 22.02.2003, 00:00 by Chiung-Cheng Huang, Ying-Chih Lin, Shou-Ling Huang, Yi-Hong Liu, Yu Wang
Dinuclear ruthenium cyclopropenyl complexes ([Ru] = (η5-C5H5)(PPh3)2Ru, R = CN, 3a; R = CH2CH2, 3b; R = Ph, 3c) are prepared by deprotonation of corresponding vinylidene complexes {[Ru]CC(CH2R)}2C6H42+ (2). For the vinylidene complex 2d (R = CO2Me) with an ester group, the deprotonation reaction leads to formation of the dinuclear bis-furyl complex (5d). Electrophilic addition of TCNQ to both three-membered rings of 3a yields the zwitterionic bis-vinylidene complex {[Ru]CC[CH(TCNQ)CN]}2C6H4 (4a), which, in the presence of MeOH/n-Bu4NOH, gives the methoxy-substituted bis-cyclopropenyl complex (6a). The proton-induced demethoxylation of 6a generates (7a). The reaction of TMSN3 with 3a gives the bis-tetrazolate complex {[Ru](N4C)CH(CH2CN)}2C6H4 (8a). Trinuclear tris-cyclopropenyl complexes (R = CN, 11a; R = CH2CH2, 11b; R = Ph, 11c) are obtained from deprotonation of {1,3,5-{[Ru]CC(CH2R)C6H4C⋮C}3C6H3}3+ (10). Complex 2b is characterized by X-ray diffraction analysis, and other complexes are characterized by spectroscopic methods.