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Reactivity of ruthenium complexes with uninegative (X,S)-donor ligands (X = S,P)—II. Phosphine substitution in [Ru(S,S)2(PR3)2] derivatives. Crystal structure of trans-bis(O-ethyldithiocarbonate)bis(dimethylphenylphosphine)-ruthenium(II) |
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| Authors: | Loreto Ballester Oscar Esteban Angel Gutierrez Maria Felisa Perpi an Caridad Ruiz-Valero Enrique Gutierrez-PueblaMaria Jesus Gonzalez |
| Affiliation: | Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense, 28040- Madrid, Spain Laboratorio de Difracción de Rayos-X, Facultad de Ciencias Químicas, Universidad Complutense e Instituto de Ciencia de los Materiales, Sede D, C.S.I.C., Serrano 113, 28006- Madrid, Spain Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad del País Vasco, Apartado 1072, 20080- San Sebastian, Spain |
| Abstract: | The complexes [Ru(S,S)2(PPh3)2] [S,S = EtCOCS2−, (CH2)4NCS2−] react with a variety of tertiary phosphines with the substitution of triphenylphosphine and the formation of [Ru(S,S)2(PR3)2]. The reaction occurs with the formation ofthe cis isomer, except for the complex with PMe2Ph that gives rise to the trans isomer as the crystal structure shows. The effect of the different phosphines on the ruthenium complex is analysed in terms of the spectroscopic and electrochemical properties of the isolated compounds. The cyclic voltammetric studies of the cis complexes show that isomerization to the trans isomer occurs on oxidation. This isomerization is not observed in the trans-[Ru(S,S)2(PMe2Ph)2] complexes that give rise to stable trans-ruthenium(II)/ruthenium(III) couples. In a similar way the diphosphine complexes afford a quasi-reversible cis-ruthenium(II)/ruthenium(III) process. |
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