243473-63-4Relevant academic research and scientific papers
Cyclization Reactions of Ruthenium Vinylidene Complexes
Chang, Chao-Wan,Lin, Ying-Chih,Lee, Gene-Hsiang,Wang, Yu
, p. 3445 - 3450 (2008/10/08)
Treatment of [Ru]-C=C(Ph)C(=NPh)S (2, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2-CH2PPh2) with ICH2CN at room temperature affords the S-alkylation product [Ru]=C= C(Ph)C(=NPh)SCH2R+ (3a, R = CN). Deprotonation of 3a by n-Bu4NOH in acetone induces a novel cyclization reaction and yields the neutral five-membered-ring heterocyclic complex [Ru]-C=C(Ph)C(=NPh)SCHCN (5a), which isomerizes to the 2-aminothiophene complex [Ru]-C=C(CN)SC(NHPh)=C(Ph) (6a). Treatment of 2 with organic bromides BrCH2R affords both S-alkylation products (3b, R = CO2CH3; 3c, R = p-C6H4CN; 3d, R = Ph) and N-alkylation products [Ru]=C=C(Ph)C(=S)NPhCH2R+ (4b, R = CO2CH3; 4c, R = p-C6H4CN; 4d, R = Ph) in varying ratios. Base-induced cyclization of a mixture of 3b and 4b occurs only for the 3b component to afford [Ru]-C=C(Ph)CC=NPh)SCHCO2CH3 (5b), whereas cyclization of a mixture of 3c and 4c occurs for both complexes, yielding 5c and the pyrrole-2-thione complex [Ru]-C=C(Ph)C(=S)N(Ph)CH(p-C6H4CN) (7c), respectively. Cyclization of a 3d-4d mixture occurs only for 4d to afford [Ru]-C=C(Ph)C(=S)NPhCHPh (7d). The structures of 6a and 7c were determined by single-crystal X-ray diffraction analysis.
