(Ethene)bis(acetylacetonato) complexes of divalent and trivalent ruthenium

Zinc dust reduction of tris(acetylacetonato)ruthenium(III), [Ru(acac)(3)], in hot aqueous THF in the presence of ethene gives cis-[Ru(acac)(2)(eta(2)-C2H4)(2)] (5), isolated as an orange solid in ca. 60% yield. A single-crystal X-ray crystallographic study shows the metal atom to be coordinated octahedrally by a pair of bidentate O-bonded acac groups and two mutually cis orthogonal ethene ligands. In the NMR spectra of 5, the ethene carbon atoms remain equivalent, while the protons are inequivalent in pairs, down to -95 degreesC; intermolecular exchange with ethene is slow on the NMR time scale at room temperature but becomes fast above ca. 80 C. One of the ethene molecules of 5 is replaced by ligands at room temperature to give [Ru(acac)(2)eta(2)-C2H4)(L)] [L = SbPh3 (6), MeCN (7), NH3 (8), and C5H5N (9)]. Complexes\ 6 and 7 are isolated as cis-isomers, 9 as a cis-trans mixture, and 8 in the form of the transisomer which transforms into the cis-isomer when heated or chromatographed on alumina. The structures of cis-8 and trans-9 have been confirmed by X-ray crystallography. The results indicate that ligand substitutions on 5 may occur via a square pyramidal intermediate [Ru(acac)2( eta(2)-C2H4)] in which ethene occupies the apical site. All the complexes display either a quasi-reversible or a fully reversible one-electron oxidation by cyclic voltammetry at -50 C, with Eve values in the range +0.37-0.59 V for 6-9 and +0.95 V for 5 (in 0.5 M [Bu4N]PF6/ CH2Cl2 vs Ag/AgCl/MeCN). The blue oxidized species 5(+), 6(+), and 8(+) can be generated by bulk electrolysis and are stable for hours at -50 C. Their UV-vis spectra and the ESR spectra of 6(+) and 8(+) indicate that the oxidized species are ruthenium(III)-ethene cations. Oxidation of the known cyclooctene complex cis-[Ru(acac)(2)(eta(7) 2-C8H14)(SbPh3)] (2) with AgPF6 at -50 degreesC gives an isolable, deep blue ruthenium(III) salt [2](+)[PF6](-), which is stable at room temperature.