Reactivities and structural and electrochemical studies of coordinatively unsaturated arene(dithiolato)Ru(II) complexes

Je Hong Won, Hong Gyu Lim, Bo Young Kim, Jong Dae Lee, Chongmok Lee, Young Joo Lee, Sungil Cho, Jaejung Ko, Sang Ook Kang

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27 Scopus citations


The addition reactions of 16-electron complexes [(η6-arene)Ru(CabS,S′)] [3: arene = p-cymene (3a), C6Me6 (3b); CabS,S′ = 1,2-S2C2B10H10-S,S′] with the nucleophiles PEt3, CNBut, and CO lead to the formation of the corresponding 18-electron complexes 4-6 [(η6-arene)-Ru(CabS,S′)(L)] (L = PEt3, CNBut, CO), which have been characterized by X-ray crystallography. Investigation of the redox process in a series of these base-adduct metalladithiolene complexes by cyclic voltammetry reveals a large dependence of the redox potentials on the nature of the ancillary η6-arene and incoming L ligand. In an analogous manner, the reactivity of 3a toward arylamines (7) has been found to produce [(η6-p-cymene)Ru(CabS,S′)-(L)] (8) [L = η1-NH2(CH2CH2)Ar, Ar = C6H5 (8a); C6H4OMe (8b); C6H3(OMe)2 (8c); C8H6N (8d)], having molecular structures closely related to those of 4 and 5, as deduced by an electrochemical analysis and NMR studies. In addition, complex 3 reacts with a variety of substrates such as alkynes and a diazoalkane, generating a new class of dithiolato ruthenium-(II) complexes incorporating alkene and alkylidene units. Thus, the syntheses of the half-sandwich ruthenium(II) complexes [(η6-arene)Ru{η3-(S,S,C′)-SC2B 10H10SC′R2}] [C′R2 = (COOMe)C=C(COOMe) (9: arene = p-cymene (9a), C6Me6 (9b)), HC=CPh (10: arene = C6Me6 (10b)), CH2SiMe3 (11: arene = p-cymene (11a), C6Me6 (11b))] are reported, and the structure of lib has been established by an X-ray diffraction study. The formation of 9 and 10 has also been electrochemically investigated.

Original languageEnglish
Pages (from-to)5703-5712
Number of pages10
Issue number26
StatePublished - 23 Dec 2002


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