197166-48-6Relevant academic research and scientific papers
Ferrocene-containing (η6-Hexamethylbenzene)ruthenium(II) methoxycarbenes: Synthesis, structure, and electrochemistry
?těpni?ka, Petr,Gyepes, Róbert,Lavastre, Olivier,Dixneuf, Pierre H.
, p. 5089 - 5095 (1997)
The (η6-hexamethylbenzene)dichlororuthenium(II) complexes [(η6-C6Me6)RuCl2(L)], where L = PMe3 (1), PPh3 (2), FcPPh2 (3; Fc = ferrocenyl), and Hdpf (4; Hdpf = (η5-C5H4PPh2)Fe(η 5-C5H4COOH)), were reacted with terminal alkynes (FcC≡CH, Me3SiC≡CH, and PhC≡CH) in the presence of NaPF6 and methanol to give (η6-hexamethylbenzene)chlororuthenium(II) methoxycarbenes [(η6-C6Me6)RuC=C(OCH3)CH 2R)Cl(L)]PF6 (L/R = PMe3/Fc (1a), PPh3/Fc (2a), FcPPh2/Fc (3a), FcPPh2/H (3b), FcPPh2/Ph (3c), Hdpf/Fc (4a), Hdpf/H (4b), and Hdpf/ Ph (4c)). All new compounds were characterized by NMR and IR spectroscopy and also studied by mass spectrometry in liquid matrix. The solid-state structure of 4a·CH2Cl2 was determined by single-crystal X-ray diffraction. The electrochemical study of these bi- and trimetallic complexes displayed that upon oxidation, the Ru-ferrocenyl phosphine moiety undergoes a ferrocene/ferrocenium redox process followed by a Ru(II) → Ru(III) oxidation which is, however, markedly influenced by the preceding redox change. A redox dissymmetry of carbenes 1a-4c was observed, as these exhibit communication within the Ru-phosphine part while the carbene ferrocenyl group remains isolated and practically unaffected.
