Paramagnetic Precursors for Supramolecular Assemblies: Selective Syntheses, Crystal Structures, and Electrochemical and Magnetic Properties of Ru2(O2CMe)4-n(formamidinate)nCl Complexes, n = 1−4
datasetposted on 27.12.2004 by Panagiotis Angaridis, F. Albert Cotton, Carlos A. Murillo, Dino Villagrán, Xiaoping Wang
Datasets usually provide raw data for analysis. This raw data often comes in spreadsheet form, but can be any collection of data, on which analysis can be performed.
Reactions of Ru2(O2CMe)4Cl with two formamidines, HDXyl2,6F = N,N‘-di(2,6-xylyl)formamidine and HDAniF = N,N‘-di(p-anisyl)formamidine, have been investigated with the idea of synthesizing compounds with a mixed set of ligands having different labilities to be used as precursors of paramagnetic, higher-order assemblies. Depending on the formamidine and the reaction conditions, several Ru25+ compounds of the type Ru2(O2CMe)4-n(DArF)nCl (DArF = anion of an N,N‘-diarylformamidine) have been isolated. With the bulky formamidine HXyl2,6F, the compounds Ru2(O2CMe)3(DXyl2,6F)Cl (1) and trans-Ru2(O2CMe)2(DXyl2,6F)2Cl (2) were obtained. From reactions with appropriate amounts of HDAniF in THF and in the presence of NEt3 and LiCl, complexes of the general type Ru2(O2CMe)4-n(DArF)nCl (n = 1−4) were selectively obtained. For n = 2, only the cis isomer was obtained. The choice of solvent in reactions of Ru2(O2CMe)4Cl and HDAniF is of great importance. Toluene favored the formation of the fully substituted Ru25+ complex Ru2(DAniF)4Cl (3), whereas MeOH resulted in a disproportionation reaction that gave the edge-sharing bioctahedral Ru3+Ru3+ complex [trans-Ru2(μ-OMe)2(μ-O2CMe)2(HDAniF)4]Cl2 (6) and the Ru24+ complex Ru2(DAniF)4 (7). Complexes 6 and 7 with an Ru26+ and Ru24+ core, respectively, are diamagnetic, whereas all Ru25+ complexes are paramagnetic with σ2π4δ2(π*δ*)3 ground-state electronic configurations and large zero-field splitting contributions. All compounds show rich and complex electrochemical behavior.