6 research outputs found
Structures of 1,1ā²,3,3ā²-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1ā) 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 1,1ā²,3,3ā²-tetraĀ(2-methyl-2-nonyl)Āferrocene
(DEC) and the oxoanion ferrocenium salts DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup> were determined
by single-crystal X-ray diffraction. The four structures are similar
except that the three DEC<sup>+</sup> salts have layers of XO<sub><i>n</i></sub><sup>ā</sup> 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 Ć
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The structures also contain
layers of rigorously coplanar Fe and X atoms that are tilted 65.4,
75.9, 61.9, and 61.1Ā° from the aforementioned layers of Fe atoms
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The local environments
of the XO<sub><i>n</i></sub><sup>ā</sup> oxoanions
consist of networks of CāHĀ·Ā·Ā·O hydrogen bonds,
and the structures exhibit channels through which these anions could
diffuse. Facile diffusion of these anions in thin films of DEC<sup>+</sup>XO<sub><i>n</i></sub><sup>ā</sup>, with structures
that appear to resemble the crystal structures, has been demonstrated
Structures of 1,1ā²,3,3ā²-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1ā) 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 1,1ā²,3,3ā²-tetraĀ(2-methyl-2-nonyl)Āferrocene
(DEC) and the oxoanion ferrocenium salts DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup> were determined
by single-crystal X-ray diffraction. The four structures are similar
except that the three DEC<sup>+</sup> salts have layers of XO<sub><i>n</i></sub><sup>ā</sup> 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 Ć
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The structures also contain
layers of rigorously coplanar Fe and X atoms that are tilted 65.4,
75.9, 61.9, and 61.1Ā° from the aforementioned layers of Fe atoms
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The local environments
of the XO<sub><i>n</i></sub><sup>ā</sup> oxoanions
consist of networks of CāHĀ·Ā·Ā·O hydrogen bonds,
and the structures exhibit channels through which these anions could
diffuse. Facile diffusion of these anions in thin films of DEC<sup>+</sup>XO<sub><i>n</i></sub><sup>ā</sup>, with structures
that appear to resemble the crystal structures, has been demonstrated
Structures of 1,1ā²,3,3ā²-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1ā) 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 1,1ā²,3,3ā²-tetraĀ(2-methyl-2-nonyl)Āferrocene
(DEC) and the oxoanion ferrocenium salts DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup> were determined
by single-crystal X-ray diffraction. The four structures are similar
except that the three DEC<sup>+</sup> salts have layers of XO<sub><i>n</i></sub><sup>ā</sup> 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 Ć
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The structures also contain
layers of rigorously coplanar Fe and X atoms that are tilted 65.4,
75.9, 61.9, and 61.1Ā° from the aforementioned layers of Fe atoms
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The local environments
of the XO<sub><i>n</i></sub><sup>ā</sup> oxoanions
consist of networks of CāHĀ·Ā·Ā·O hydrogen bonds,
and the structures exhibit channels through which these anions could
diffuse. Facile diffusion of these anions in thin films of DEC<sup>+</sup>XO<sub><i>n</i></sub><sup>ā</sup>, with structures
that appear to resemble the crystal structures, has been demonstrated
Structures of 1,1ā²,3,3ā²-Tetra(2-methyl-2-nonyl)ferrocenium(1+) Oxoanion(1ā) 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 1,1ā²,3,3ā²-tetraĀ(2-methyl-2-nonyl)Āferrocene
(DEC) and the oxoanion ferrocenium salts DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup> were determined
by single-crystal X-ray diffraction. The four structures are similar
except that the three DEC<sup>+</sup> salts have layers of XO<sub><i>n</i></sub><sup>ā</sup> 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 Ć
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The structures also contain
layers of rigorously coplanar Fe and X atoms that are tilted 65.4,
75.9, 61.9, and 61.1Ā° from the aforementioned layers of Fe atoms
for DEC, DEC<sup>+</sup>NO<sub>3</sub><sup>ā</sup>, DEC<sup>+</sup>ClO<sub>4</sub><sup>ā</sup>, and DEC<sup>+</sup>ReO<sub>4</sub><sup>ā</sup>, respectively. The local environments
of the XO<sub><i>n</i></sub><sup>ā</sup> oxoanions
consist of networks of CāHĀ·Ā·Ā·O hydrogen bonds,
and the structures exhibit channels through which these anions could
diffuse. Facile diffusion of these anions in thin films of DEC<sup>+</sup>XO<sub><i>n</i></sub><sup>ā</sup>, with structures
that appear to resemble the crystal structures, has been demonstrated
Synthesis and Characterization of [Ir(1,5-Cyclooctadiene)(Ī¼-H)]<sub>4</sub>: A Tetrametallic Ir<sub>4</sub>H<sub>4</sub>-Core, Coordinatively Unsaturated Cluster
Reported herein is the synthesis of the previously unknown
[IrĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub> (where 1,5-COD = 1,5-cyclooctadiene),
from commercially available
[IrĀ(1,5-COD)ĀCl]<sub>2</sub> and LiBEt<sub>3</sub>H <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 UVāvis, IR, and nuclear magnetic resonance (NMR)
spectroscopies. The resultant product parallelsīøbut the successful
synthesis is different from, vide infraīøthat of the known and
valuable Rh congener precatalyst and synthon, [RhĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub>. Extensive characterization reveals that a black crystal
of [IrĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub> is composed of a distorted
tetrahedral, <i>D</i><sub>2<i>d</i></sub> symmetry
Ir<sub>4</sub> core with two long [2.90728(17) and 2.91138(17) Ć
]
and four short IrāIr [2.78680 (12)ā2.78798(12) Ć
]
bond distances. One 1,5-COD and two edge-bridging hydrides are bound
to each Ir atom; the IrāHāIr span the shorter IrāIr
bond distances. XAFS provides excellent agreement with the XRD-obtained
Ir<sub>4</sub>-core structure, results which provide both considerable
confidence in the XAFS methodology and set the stage for future XAFS
in applications employing this Ir<sub>4</sub>H<sub>4</sub> and related
tetranuclear clusters. The [IrĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub> complex
is of interest for at least five reasons, as detailed in the Conclusions
section
Synthesis and Characterization of [Ir(1,5-Cyclooctadiene)(Ī¼-H)]<sub>4</sub>: A Tetrametallic Ir<sub>4</sub>H<sub>4</sub>-Core, Coordinatively Unsaturated Cluster
Reported herein is the synthesis of the previously unknown
[IrĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub> (where 1,5-COD = 1,5-cyclooctadiene),
from commercially available
[IrĀ(1,5-COD)ĀCl]<sub>2</sub> and LiBEt<sub>3</sub>H <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 UVāvis, IR, and nuclear magnetic resonance (NMR)
spectroscopies. The resultant product parallelsīøbut the successful
synthesis is different from, vide infraīøthat of the known and
valuable Rh congener precatalyst and synthon, [RhĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub>. Extensive characterization reveals that a black crystal
of [IrĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub> is composed of a distorted
tetrahedral, <i>D</i><sub>2<i>d</i></sub> symmetry
Ir<sub>4</sub> core with two long [2.90728(17) and 2.91138(17) Ć
]
and four short IrāIr [2.78680 (12)ā2.78798(12) Ć
]
bond distances. One 1,5-COD and two edge-bridging hydrides are bound
to each Ir atom; the IrāHāIr span the shorter IrāIr
bond distances. XAFS provides excellent agreement with the XRD-obtained
Ir<sub>4</sub>-core structure, results which provide both considerable
confidence in the XAFS methodology and set the stage for future XAFS
in applications employing this Ir<sub>4</sub>H<sub>4</sub> and related
tetranuclear clusters. The [IrĀ(1,5-COD)Ā(Ī¼-H)]<sub>4</sub> complex
is of interest for at least five reasons, as detailed in the Conclusions
section