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

Title
Reactivities and structural and electrochemical studies of coordinatively unsaturated arene(dithiolato)Ru(II) complexes
Authors
Won J.-H.Lim H.-G.Kim B.Y.Lee J.-D.Lee C.Lee Y.-J.Cho S.Ko J.Kang S.O.
Ewha Authors
이종목
SCOPUS Author ID
이종목scopus
Issue Date
2002
Journal Title
Organometallics
ISSN
0276-7333JCR Link
Citation
vol. 21, no. 26, pp. 5703 - 5712
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
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.
DOI
10.1021/om020259l
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자연과학대학 > 화학·나노과학전공 > Journal papers
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