Barral M C, Jiménez-Aparicio R, Pérez-Quintanilla D, Priego J L, Royer E C, Torres M R, Urbanos F A
Departamento de Química Inorgánica and Centro de Asistencia a la Investigación de Rayos X, Facultad de Ciencias Químicas, Universidad Complutense, Ciudad Universitaria, 28040 Madrid, Spain.
Inorg Chem. 2000 Jan 10;39(1):65-70. doi: 10.1021/ic9907462.
The reaction of Ru2Cl(mu-O2CMe)4 with 2,4-hexadienoic and 2-methoxyacetic acids affords the compounds Ru2Cl(mu-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) A, b = 12.661(8) A, c = 12.839(5) A, alpha = 106.09(3) degrees, beta = 77.89(2) degrees, gamma = 97.73(3) degrees, and Z = 2. 2 crystallizes in the nonstandard monoclinic space group P2(1)/c with a = 12.132(4) A, b = 11.570(2) A, c = 13.674(2) A, beta = 91.18(2) degrees, and Z = 4. Complexes 1 and 2 show [Ru2(mu-O2CR)4]+ units linked by chloride ions, giving zigzag chains with Ru-Cl-Ru angles of 119.43(4) degrees and 110.11(7) degrees, respectively. The Ru-Ru bond distances are 2.2857(9) A (1) and 2.290(1) A (2). A magnetic study, in the 2-300 K temperature range, of the new compounds and the previously described Ru2Cl(mu-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.
Ru2Cl(μ - O2CMe)4 与 2,4 - 己二烯酸和 2 - 甲氧基乙酸反应生成化合物 Ru2Cl(μ - O2CR)4 [R = CH=CHCH=CHCH3 (1), CH2OMe (2)]。两种配合物的结构均已通过 X 射线晶体学确定。1 以三斜空间群 P - 1 结晶，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)°，Z = 2。2 以非标准单斜空间群 P2(1)/c 结晶，a = 12.132(4) Å，b = 11.570(2) Å，c = 13.674(2) Å，β = 91.18(2)°，Z = 4。配合物 1 和 2 显示出由氯离子连接的 [Ru2(μ - O2CR)4]+ 单元，形成之字形链，Ru - Cl - Ru 角分别为 119.43(4)° 和 110.11(7)°。Ru - Ru 键长分别为 2.2857(9) Å (1) 和 2.290(1) Å (2)。描述了在 2 - 300 K 温度范围内对新化合物以及先前描述的 Ru2Cl(μ - O2CR)4 [R = CHMe2 (3), CMe3 (4), C4H4N (5)] 的磁性研究。聚合物配合物 1 和 2 以及非聚合物 3 - 5 显示出较大的零场分裂，范围从 53.9 到 68.1 cm - 1。这些配合物还显示出一种微弱但不可忽略的通过空间的分子间反铁磁耦合，这在先前对这些类型化合物进行的磁性研究中未观察到。
