Magnetic Properties of Diruthenium(II,III) Carboxylate Compounds. Crystal Structures of Ru2Cl(μ-O2CCHCHCHCHMe)4 and Ru2Cl(μ-O2CCH2OMe)4

• Published in: Inorganic chemistry Vol. 39; no. 1; pp. 65 - 70
• Main Authors: Barral, M. C, Jiménez-Aparicio, R, Pérez-Quintanilla, D, Priego, J. L, Royer, E. C, Torres, M. R, Urbanos, F. A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.01.2000
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic9907462

The reaction of Ru2Cl(μ-O2CMe)4 with 2,4-hexadienoic and 2-methoxyacetic acids affords the compounds Ru2Cl(μ-O2CR)4 [R = CHCHCHCHCH3 (1), CH2OMe (2)]. The structures of both complexes have been determined by X-ray crystallography. 1 crystallizes in the triclinic space group P-1 with a = 9.264(1) Å, b = 12.661(8) Å, c = 12.839(5) Å, α = 106.09(3)°, β = 77.89(2)°, γ = 97.73(3)°, and Z = 2. 2 crystallizes in the nonstandard monoclinic space group P2(1)/c with a = 12.132(4) Å, b = 11.570(2) Å, c = 13.674(2) Å, β = 91.18(2)°, and Z = 4. Complexes 1 and 2 show [Ru2(μ-O2CR)4]+ units linked by chloride ions, giving zigzag chains with Ru−Cl−Ru angles of 119.43(4)° and 110.11(7)°, respectively. The Ru−Ru bond distances are 2.2857(9) Å (1) and 2.290(1) Å (2). A magnetic study, in the 2−300 K temperature range, of the new compounds and the previously described Ru2Cl(μ-O2CR)4 [R = CHMe2 (3), CMe3 (4), C4H4N (5)] is described. The polymeric complexes 1 and 2 and the nonpolymeric 3−5 show a large zero-field splitting which varies from 53.9 to 68.1 cm-1. These complexes also show a weak, but not negligible, through-space intermolecular antiferromagnetic coupling not observed in the previous magnetic studies carried out on these types of compounds.