Jiménez-Aparicio R, Urbanos F A, Arrieta J M
Departamento de Química Inorgánica and Sección Departamental de Matemática Aplicada, Facultad de Ciencias Químicas, Universidad Complutense, Ciudad Universitaria, 28040 Madrid, Spain.
Inorg Chem. 2001 Feb 12;40(4):613-9. doi: 10.1021/ic0001154.
The magnetic properties of mixed-valent compounds of general formula Ru2Cl(mu-O2CR)4 [R = CH2-CH3 (1), C(Me)=CHEt) (2)] have been studied in the 2-300 K temperature range. This magnetic study also includes a revision of the magnetic properties of the complex Ru2Cl(mu-O2CCMePh2)4 (3). Compounds 1-3 show a linear structure and a strong antiferromagnetic coupling between the diruthenium units through the chlorine atoms according to previous studies. Two fitting models to explain the magnetic properties of these complexes that incorporate a large zero-field splitting together with a strong antiferromagnetic coupling are described. These models consider that each diruthenium unit (S = 3/2) is magnetically coupled to the nearest diruthenium unit and ignores the longer distance magnetic coupling. The fitting models were found to be successful in fitting the magnetic data of the linear diruthenium(II,III) complexes. The zero-field splitting, D, and the antiferromagnetic coupling, zJ, vary from 37.8 to 48.0 cm-1 and from -7.43 to -13.30 cm-1, respectively, for complexes. The D values are similar to those calculated for the nonlinear diruthenium(II,III) compounds and confirm the validity of the proposed fitting models.
通式为Ru2Cl(μ - O2CR)4 [R = CH2 - CH3 (1), C(Me)=CHEt) (2)] 的混合价化合物的磁性在2 - 300 K温度范围内进行了研究。该磁性研究还包括对配合物Ru2Cl(μ - O2CCMePh2)4 (3)磁性的修正。根据先前的研究，化合物1 - 3呈现线性结构，且通过氯原子在二钌单元之间存在强反铁磁耦合。描述了两种用于解释这些配合物磁性的拟合模型，这些模型包含大的零场分裂以及强反铁磁耦合。这些模型认为每个二钌单元（S = 3/2）与最近的二钌单元磁耦合，而忽略了更长距离的磁耦合。发现拟合模型成功地拟合了线性二钌（II,III）配合物的磁性数据。对于这些配合物，零场分裂D和反铁磁耦合zJ分别在37.8至48.0 cm-1和 - 7.43至 - 13.30 cm-1之间变化。D值与为非线性二钌（II,III）化合物计算的值相似，证实了所提出拟合模型的有效性。
