Linear Inverse Sandwich Complexes of Tetraanionic Benzene Stabilized by Covalent δ-Bonding with Late Lanthanides.

A series of dilanthanide benzene inverse sandwich complexes of the type (CpLn)(μ-η:η-CH) () (Ln = Y, Gd, Tb, Dy, Tm) are reported. These compounds are synthesized by reduction of the respective trivalent dimers CpLnI (Ln = Y, Gd, Tb, Dy, Tm) in diethyl ether with potassium graphite in the presence of benzene, and they feature an unusual linear coordination geometry with a highly planar benzene bridge as verified by single-crystal X-ray diffraction. The Ln-Bz distances of are the shortest distances observed to date, ranging from 1.

Electronic Structures, Spectroscopy, and Electrochemistry of [M(diimine)(CN-BR)] (M = Fe, Ru; R = Ph, CF) Complexes.

Complexes with the formula [M(diimine)(CN-BR)], where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, CF, and M = Fe, Ru, were synthesized and characterized by X-ray crystal structure analysis, UV-visible spectroscopy, IR spectroscopy, and voltammetry. Three highly soluble complexes, [Fe(bpy)(CN-B(CF))], [Ru(bpy)(CN-B(CF))], and [Ru(flpy)(CN-B(CF))], exhibit electrochemically reversible redox reactions, with large potential differences between the bpy or flpy and M couples of 3.27, 3.

Structure, Spectroscopy, and Electrochemistry of Manganese(I) and Rhenium(I) Quinoline Oximes.

Reactions of α- and β-diimine quinoline aldoximes with Mn(I) and Re(I) tricarbonyl halides afford quinoline oxime complexes. Both Mn(I) and Re(I) complexes experience severe geometric strain due to ligand steric interactions: 6-membered metallocycles exhibit more pronounced distortions than 5-membered ones, consistent with density functional theory structural analyses. Such distortions likely also affect reactivity patterns, as evidenced by Re(I)-induced deoximation of a quinoline variant containing a CF-ketoxime.