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

Synthesis and Characterization of [Ir(1,5-Cyclooctadiene)(μ-H)]₄: A Tetrametallic Ir₄H₄-Core, Coordinatively Unsaturated Cluster

Reported herein is the synthesis of the previously unknown [Ir­(1,5-COD)­(μ-H)]₄ (where 1,5-COD = 1,5-cyclooctadiene), from commercially available [Ir­(1,5-COD)­Cl]₂ and LiBEt₃H <i>in the presence of excess 1,5-COD</i> in 78% initial, and 55% recrystallized, yield plus its unequivocal characterization via single-crystal X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, electrospray/atmospheric pressure chemical ionization mass spectrometry (ESI-MS), and UV–vis, IR, and nuclear magnetic resonance (NMR) spectroscopies. The resultant product parallelsbut the successful synthesis is different from, vide infrathat of the known and valuable Rh congener precatalyst and synthon, [Rh­(1,5-COD)­(μ-H)]₄. Extensive characterization reveals that a black crystal of [Ir­(1,5-COD)­(μ-H)]₄ is composed of a distorted tetrahedral, <i>D</i>_2<i>d</i> symmetry Ir₄ core with two long [2.90728(17) and 2.91138(17) Å] and four short Ir–Ir [2.78680 (12)–2.78798(12) Å] bond distances. One 1,5-COD and two edge-bridging hydrides are bound to each Ir atom; the Ir–H–Ir span the shorter Ir–Ir bond distances. XAFS provides excellent agreement with the XRD-obtained Ir₄-core structure, results which provide both considerable confidence in the XAFS methodology and set the stage for future XAFS in applications employing this Ir₄H₄ and related tetranuclear clusters. The [Ir­(1,5-COD)­(μ-H)]₄ complex is of interest for at least five reasons, as detailed in the Conclusions section

Synthesis and Characterization of [Ir(1,5-Cyclooctadiene)(μ-H)]₄: A Tetrametallic Ir₄H₄-Core, Coordinatively Unsaturated Cluster

Reported herein is the synthesis of the previously unknown [Ir­(1,5-COD)­(μ-H)]₄ (where 1,5-COD = 1,5-cyclooctadiene), from commercially available [Ir­(1,5-COD)­Cl]₂ and LiBEt₃H <i>in the presence of excess 1,5-COD</i> in 78% initial, and 55% recrystallized, yield plus its unequivocal characterization via single-crystal X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, electrospray/atmospheric pressure chemical ionization mass spectrometry (ESI-MS), and UV–vis, IR, and nuclear magnetic resonance (NMR) spectroscopies. The resultant product parallelsbut the successful synthesis is different from, vide infrathat of the known and valuable Rh congener precatalyst and synthon, [Rh­(1,5-COD)­(μ-H)]₄. Extensive characterization reveals that a black crystal of [Ir­(1,5-COD)­(μ-H)]₄ is composed of a distorted tetrahedral, <i>D</i>_2<i>d</i> symmetry Ir₄ core with two long [2.90728(17) and 2.91138(17) Å] and four short Ir–Ir [2.78680 (12)–2.78798(12) Å] bond distances. One 1,5-COD and two edge-bridging hydrides are bound to each Ir atom; the Ir–H–Ir span the shorter Ir–Ir bond distances. XAFS provides excellent agreement with the XRD-obtained Ir₄-core structure, results which provide both considerable confidence in the XAFS methodology and set the stage for future XAFS in applications employing this Ir₄H₄ and related tetranuclear clusters. The [Ir­(1,5-COD)­(μ-H)]₄ complex is of interest for at least five reasons, as detailed in the Conclusions section