Structures of 1,1′,3,3′-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1−) Salts. Layered Materials with Alternating Ionic and Low-Dielectric Paraffin-Like Domains Through Which Anion Diffusion is Rapid

The unprecedented interdigitated and layered structures of 1,1′,3,3′-tetra­(2-methyl-2-nonyl)­ferrocene (DEC) and the oxoanion ferrocenium salts DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^– were determined by single-crystal X-ray diffraction. The four structures are similar except that the three DEC⁺ salts have layers of XO_<i>n</i>^– oxoanions stuffed between the layers of interdigitated ferrocenium ions. The perpendicular distances between layers of Fe atoms are 8.530, 9.108, 9.009, and 9.158 Å for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The structures also contain layers of rigorously coplanar Fe and X atoms that are tilted 65.4, 75.9, 61.9, and 61.1° from the aforementioned layers of Fe atoms for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The local environments of the XO_<i>n</i>^– oxoanions consist of networks of C–H···O hydrogen bonds, and the structures exhibit channels through which these anions could diffuse. Facile diffusion of these anions in thin films of DEC⁺XO_<i>n</i>^–, with structures that appear to resemble the crystal structures, has been demonstrated

Structures of 1,1′,3,3′-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1−) Salts. Layered Materials with Alternating Ionic and Low-Dielectric Paraffin-Like Domains Through Which Anion Diffusion is Rapid

The unprecedented interdigitated and layered structures of 1,1′,3,3′-tetra­(2-methyl-2-nonyl)­ferrocene (DEC) and the oxoanion ferrocenium salts DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^– were determined by single-crystal X-ray diffraction. The four structures are similar except that the three DEC⁺ salts have layers of XO_<i>n</i>^– oxoanions stuffed between the layers of interdigitated ferrocenium ions. The perpendicular distances between layers of Fe atoms are 8.530, 9.108, 9.009, and 9.158 Å for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The structures also contain layers of rigorously coplanar Fe and X atoms that are tilted 65.4, 75.9, 61.9, and 61.1° from the aforementioned layers of Fe atoms for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The local environments of the XO_<i>n</i>^– oxoanions consist of networks of C–H···O hydrogen bonds, and the structures exhibit channels through which these anions could diffuse. Facile diffusion of these anions in thin films of DEC⁺XO_<i>n</i>^–, with structures that appear to resemble the crystal structures, has been demonstrated

Structures of 1,1′,3,3′-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1−) Salts. Layered Materials with Alternating Ionic and Low-Dielectric Paraffin-Like Domains Through Which Anion Diffusion is Rapid

The unprecedented interdigitated and layered structures of 1,1′,3,3′-tetra­(2-methyl-2-nonyl)­ferrocene (DEC) and the oxoanion ferrocenium salts DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^– were determined by single-crystal X-ray diffraction. The four structures are similar except that the three DEC⁺ salts have layers of XO_<i>n</i>^– oxoanions stuffed between the layers of interdigitated ferrocenium ions. The perpendicular distances between layers of Fe atoms are 8.530, 9.108, 9.009, and 9.158 Å for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The structures also contain layers of rigorously coplanar Fe and X atoms that are tilted 65.4, 75.9, 61.9, and 61.1° from the aforementioned layers of Fe atoms for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The local environments of the XO_<i>n</i>^– oxoanions consist of networks of C–H···O hydrogen bonds, and the structures exhibit channels through which these anions could diffuse. Facile diffusion of these anions in thin films of DEC⁺XO_<i>n</i>^–, with structures that appear to resemble the crystal structures, has been demonstrated

Structures of 1,1′,3,3′-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1−) Salts. Layered Materials with Alternating Ionic and Low-Dielectric Paraffin-Like Domains Through Which Anion Diffusion is Rapid

The unprecedented interdigitated and layered structures of 1,1′,3,3′-tetra­(2-methyl-2-nonyl)­ferrocene (DEC) and the oxoanion ferrocenium salts DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^– were determined by single-crystal X-ray diffraction. The four structures are similar except that the three DEC⁺ salts have layers of XO_<i>n</i>^– oxoanions stuffed between the layers of interdigitated ferrocenium ions. The perpendicular distances between layers of Fe atoms are 8.530, 9.108, 9.009, and 9.158 Å for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The structures also contain layers of rigorously coplanar Fe and X atoms that are tilted 65.4, 75.9, 61.9, and 61.1° from the aforementioned layers of Fe atoms for DEC, DEC⁺NO₃^–, DEC⁺ClO₄^–, and DEC⁺ReO₄^–, respectively. The local environments of the XO_<i>n</i>^– oxoanions consist of networks of C–H···O hydrogen bonds, and the structures exhibit channels through which these anions could diffuse. Facile diffusion of these anions in thin films of DEC⁺XO_<i>n</i>^–, with structures that appear to resemble the crystal structures, has been demonstrated

Redox-Active Bis(phenolate) N‑Heterocyclic Carbene [OCO] Pincer Ligands Support Cobalt Electron Transfer Series Spanning Four Oxidation States

A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis­(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate complexes are best formulated as Co­(II) centers bound to closed-shell [OCO]^2– dianions, of the general formula [(OCO)­Co^IIL] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms of the [(OCO)­Co^IIL] complexes reveal three oxidations accessible at potentials below 1.2 V vs Fc⁺/Fc, corresponding to generation of formally Co­(V) species, but the true physical/spectroscopic oxidation states are much lower. Chemical oxidations afford the mono- and dications of the imidazoline NHC-derived complex, which were examined by computational and magnetic and spectroscopic methods, including single-crystal X-ray diffraction. The metal and ligand oxidation states of the monocationic complex are ambiguous; data are consistent with formulation as either [(^SOCO)­Co^III(THF)₂]⁺ containing a closed-shell [^SOCO]^2– diphenolate ligand bound to a <i>S</i> = 1 Co­(III) center, or [(^SOCO^•)­Co^II(THF)₂]⁺ with a low-spin Co­(II) ion ferromagnetically coupled to monoanionic [^SOCO^•]⁻ containing a single unpaired electron distributed across the [OCO] framework. The dication is best described as [(^SOCO⁰)­Co^II(THF)₃]²⁺, with a single unpaired electron localized on the d⁷ Co­(II) center and a doubly oxidized, charge-neutral, closed-shell ^SOCO⁰ ligand. The combined data provide for the first time unequivocal and structural evidence for [OCO] ligand redox activity. Notably, varying the degree of unsaturation in the NHC backbone shifts the ligand-based oxidation potentials by up to 400 mV. The possible chemical origins of this unexpected shift, along with the potential utility of the [OCO] pincer ligands for base-metal-mediated organometallic coupling catalysis, are discussed