The substitution chemistry of RuCp*(tmeda)Cl

摘要

Halide abstraction from RuCp*(tmeda)Cl (1, tmeda=Me2NCH2CH2NMe2) with NaBPh4 in CH2Cl2 leads to the formation of the sandwich complex RuCp*(eta 6-C6H5BPh3) (2). In the presence of CH3CN (1 equiv.) and CO, however, the cationic complexes [RuCp*(tmeda)(CH3CN)](+) (3) and [RuCp*(tmeda)(CO)](+) (5) are obtained. In CH3CN, tmeda is also replaced giving [PuCp*(CH3CN)(3)](+) (4). Complex 1 reacts readily with terminal acetylenes HC=CR, the products depending on the nature of R (Ph, SiMe3, n-Bu, COOEt). Thus, with R = Ph the ruthenacyclopentatriene complex RuCp*(sigma,sigma'-C4Ph2H2)Cl (6), with R=SiMe3 the cyclobutadiene complex Ru(Cp*)(eta(4)-C4H2(1,2-SiMe3)(2))Cl (7), and with R=n-Bu and COOEt the binuclear complexes (Cp*)RuCl2(eta(2):eta(4)-mu(2)-C4H2(1,3-R)(2))Ru(Cp*) (8, 9) are obtained. Furthermore, with diethyl maleate in the presence of 1 equiv. of LiCl, 1 transforms into the new anionic complex Li[Ru(Cp*) (eta(2)-C2H2(COOEt)2)Cl-2] (10). X-ray structures of 2, 3, 4, 7, and 10 are included.