Cyclization Reactions of Ruthenium Vinylidene Complexes
Resource
Organometallics 18 (17): 3445-3450
Journal
Organometallics
Journal Volume
18
Journal Issue
17
Pages
3445-3450
Date Issued
1999
Author(s)
Abstract
Treatment of (2, [Ru] = (η5-C5H5)(dppe)Ru, dppe = Ph2PCH2CH2PPh2) with ICH2CN at room temperature affords the S-alkylation product [Ru]CC(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 (5a), which isomerizes to the 2-aminothiophene complex (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]CC(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 (5b), whereas cyclization of a mixture of 3c and 4c occurs for both complexes, yielding 5c and the pyrrole-2-thione complex (7c), respectively. Cyclization of a 3d−4d mixture occurs only for 4d to afford (7d). The structures of 6a and 7c were determined by single-crystal X-ray diffraction analysis.
SDGs
Type
journal article