Summary.
The polymeric compound [Ru(cod)Cl2] x (cod = cyclooctadiene) reacts with 2 equivalents of tmeda (N,N,N′,N′-tetramethylethylenediamine) in refluxing MeOH to afford trans-[Ru(cod)(tmeda)(Cl)(H)] (1), which upon treatment with CHCl3 is readily converted to the dichloro complex trans-[Ru(cod)(tmeda)Cl2] (2). When [Ru(cod)Cl2] x is reacted with tmeda under an atmosphere of H2 (3 bar), the bis-tmeda complex trans-[Ru(tmeda)2Cl2] (3) is obtained in 80% yield. DFT calculations revealed that 3 is by 52 kJ/mol more stable than the corresponding cis isomer. Attempts to prepare the coordinatively unsaturated complex [Ru(tmeda)2Cl]+ by reacting 1 with TICF3SO3 were unsuccessful. According to DFT calculations, however, such a complex should be stable and, interestingly, should adopt a square pyramidal rather than a trigonal bipyramidal structure. If halide abstraction of 3 is performed in the presence of terminal alkynes HC*CR (R*t-Bu, n-Bu), the cationic vinylidene complexes [Ru(tmeda)2(Cl)(*C*CHR)]+ (4a,b) are obtained.
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Received March 26, 2001. Accepted April 26, 2001
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Gomez, J., Gemel, C., Slugovc, C. et al. Synthesis and Characterization of Some Ru(tmeda) Complexes Containing Chloride, Hydride, and Vinylidene Ligands. Monatshefte fuer Chemie 132, 1137–1143 (2001). https://doi.org/10.1007/s007060170029
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DOI: https://doi.org/10.1007/s007060170029