Manipulating Magnetism: Ru25+ Paddlewheels Devoid of Axial Interactions

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• 作者：Gina M. Chiarella ; F. Albert Cotton ; Carlos A. Murillo ; Karen Ventura ; Dino Villagr谩n ; Xiaoping Wang
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：July 9, 2014
• 年：2014
• 卷：136
• 期：27
• 页码：9580-9589
• 全文大小：417K
• ISSN：1520-5126

文摘

Variable-temperature magnetic and structural data of two pairs of diruthenium isomers, one pair having an axial ligand and the formula Ru₂(DArF)₄Cl (where DArF is the anion of a diarylformamidine isomer and Ar = p-anisyl or m-anisyl) and the other one being essentially identical but devoid of axial ligands and having the formula [Ru₂(DArF)₄]BF₄, show that the axial ligand has a significant effect on the electronic structure of the diruthenium unit. Variable temperature crystallographic and magnetic data as well as density functional theory calculations unequivocally demonstrate the occurrence of 蟺 interactions between the p orbitals of the chlorine ligand and the 蟺* orbitals in the Ru₂⁵⁺ units. The magnetic and structural data are consistent with the existence of combined ligand 蟽/metal 蟽 and ligand p蟺/metal-d蟺 interactions. Electron paramagnetic resonance data show unambiguously that the unpaired electrons are in metal-based molecular orbitals.