TY - JOUR
T1 - Paramagnetic precursors for supramolecular assemblies
T2 - Selective syntheses, crystal structures, and electrochemical and magnetic properties of Ru 2(O2CMe)4-n(formamidinate)nCl complexes, n = 1-4
AU - Angaridis, Panagiotis
AU - Cotton, F. Albert
AU - Murillo, Carlos A.
AU - Villagrán, Dino
AU - Wang, Xiaoping
PY - 2004/12/27
Y1 - 2004/12/27
N2 - Reactions of Ru2(O2CMe)4Cl with two formamidines, HDXyl2,6F = N,N′2,6-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 Ru 2(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(O 2CMe)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 Ru 2(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 Ru 25+ complex Ru2(DAniF)4Cl (3), whereas MeOH resulted in a disproportionation reaction that gave the edge-sharing bioctahedral Ru3+Ru3+ complex [trans- Ru 2(μ-OMe)2(μ-O2CMe)2(HDAniF) 4]Cl2 (6) and the Ru24+ complex Ru2(DAniF)4 (7). Complexes 6 and 7 with an Ru 26+ 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.
AB - Reactions of Ru2(O2CMe)4Cl with two formamidines, HDXyl2,6F = N,N′2,6-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 Ru 2(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(O 2CMe)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 Ru 2(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 Ru 25+ complex Ru2(DAniF)4Cl (3), whereas MeOH resulted in a disproportionation reaction that gave the edge-sharing bioctahedral Ru3+Ru3+ complex [trans- Ru 2(μ-OMe)2(μ-O2CMe)2(HDAniF) 4]Cl2 (6) and the Ru24+ complex Ru2(DAniF)4 (7). Complexes 6 and 7 with an Ru 26+ 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.
UR - http://www.scopus.com/inward/record.url?scp=11144352177&partnerID=8YFLogxK
U2 - 10.1021/ic049108w
DO - 10.1021/ic049108w
M3 - Article
AN - SCOPUS:11144352177
SN - 0020-1669
VL - 43
SP - 8290
EP - 8300
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 26
ER -