Iridium DMSO driver calculations

Input and output files and XYZ coordinates from driver calculations on the trans-bis(DMSO)tetrachloroiridate anion. The effect of rotation of one DMSO ligand about the Ir–S axis is investigated by DFT. B3LYP-D def2-svp on all atoms but Ir, which was treated with the Stuttgart-Dresden ECP and def2-tzvp for the valence electrons

Metallosupramolecular Chemistry of Novel Chiral <i>closo</i>-<i>o</i>‑Carboranylalcohol Pyridine and Quinoline Ligands: Syntheses, Characterization, and Properties of Cobalt Complexes

The cobalt­(II) complexes CoCl₂(LOH)₂ (LOH = 1-[R­(hydroxy)­methyl]-2-R′-1,2-dicarba-<i>closo</i>-dodecaborane (R′ = H or Me; R = 2-pyridyl <b>3a</b> or <b>4a</b>, 3-pyridyl <b>3b</b> or <b>4b</b>, 4-pyridyl <b>3c</b> or <b>4c</b>, 2-quinolyl <b>3d</b> or <b>4d</b>, 4-quinolyl <b>3e</b> or <b>4e</b>)) and CoCl₂(LOH)₄ (<b>5</b>, R′ = H; R = 4-pyridyl) were synthesized and characterized. Deprotonation of alcohol in <b>3a</b> afforded the square-planar complex Co^II(LO)₂ (<b>6</b>) that oxidized slowly in solution and under air to give the cobaltacarborane complex Co^III{(η⁵-C₂B₉H₁₀)­(CHOH)­(η¹-NC₅H₄)}­(η²-NC₅H₄COO) (<b>7</b>). Crystal structures for <b>3a</b>, <b>3a·2MeOH</b>, <b>3b</b>, <b>3e</b>, <b>4c</b>, <b>4e</b>, <b>5</b>, <b>6</b>, and <b>7</b> have been determined by X-ray diffraction (XRD). Molecular structures show octahedral (<b>3a</b>, <b>3a·2MeOH</b>, <b>5</b>), tetrahedral (<b>3b</b>, <b>3e</b>, <b>4c</b>, <b>4e</b>), and square-planar (<b>6</b>) coordination around Co^II centers, whereas 2-pyridyl and quinolyl ligands favor a bidentate <i>N</i>,<i>O</i>-coordination mode and 3- and 4-pyridyl and quinolyl ligands favor a monodentate <i>N</i>-coordination. The supramolecular structures are dominated by intermolecular O–H···Cl/O hydrogen bonds and π–π interactions in the case of tetrahedral complexes. The magnetic properties of <b>3a</b>–<b>c</b> were investigated in the temperature range 2–300 K by means of χ_M<i>T</i>, which corroborated coordination numbers and geometries as well as provided information on the supramolecular interactions among neighboring molecules for all three compounds. Complex <b>3a</b> shows solvent accessible channels running parallel to the hydrogen bonding network and is able to uptake methanol vapors to convert into <b>3a·2MeOH</b>. The structure of <b>3a</b> is related to that for <b>3a·2MeOH</b> by rotation of complex molecules within the 1D O–H···Cl hydrogen bonding networks and insertion of methanol into it

Metallosupramolecular Chemistry of Novel Chiral <i>closo</i>-<i>o</i>‑Carboranylalcohol Pyridine and Quinoline Ligands: Syntheses, Characterization, and Properties of Cobalt Complexes

The cobalt­(II) complexes CoCl₂(LOH)₂ (LOH = 1-[R­(hydroxy)­methyl]-2-R′-1,2-dicarba-<i>closo</i>-dodecaborane (R′ = H or Me; R = 2-pyridyl <b>3a</b> or <b>4a</b>, 3-pyridyl <b>3b</b> or <b>4b</b>, 4-pyridyl <b>3c</b> or <b>4c</b>, 2-quinolyl <b>3d</b> or <b>4d</b>, 4-quinolyl <b>3e</b> or <b>4e</b>)) and CoCl₂(LOH)₄ (<b>5</b>, R′ = H; R = 4-pyridyl) were synthesized and characterized. Deprotonation of alcohol in <b>3a</b> afforded the square-planar complex Co^II(LO)₂ (<b>6</b>) that oxidized slowly in solution and under air to give the cobaltacarborane complex Co^III{(η⁵-C₂B₉H₁₀)­(CHOH)­(η¹-NC₅H₄)}­(η²-NC₅H₄COO) (<b>7</b>). Crystal structures for <b>3a</b>, <b>3a·2MeOH</b>, <b>3b</b>, <b>3e</b>, <b>4c</b>, <b>4e</b>, <b>5</b>, <b>6</b>, and <b>7</b> have been determined by X-ray diffraction (XRD). Molecular structures show octahedral (<b>3a</b>, <b>3a·2MeOH</b>, <b>5</b>), tetrahedral (<b>3b</b>, <b>3e</b>, <b>4c</b>, <b>4e</b>), and square-planar (<b>6</b>) coordination around Co^II centers, whereas 2-pyridyl and quinolyl ligands favor a bidentate <i>N</i>,<i>O</i>-coordination mode and 3- and 4-pyridyl and quinolyl ligands favor a monodentate <i>N</i>-coordination. The supramolecular structures are dominated by intermolecular O–H···Cl/O hydrogen bonds and π–π interactions in the case of tetrahedral complexes. The magnetic properties of <b>3a</b>–<b>c</b> were investigated in the temperature range 2–300 K by means of χ_M<i>T</i>, which corroborated coordination numbers and geometries as well as provided information on the supramolecular interactions among neighboring molecules for all three compounds. Complex <b>3a</b> shows solvent accessible channels running parallel to the hydrogen bonding network and is able to uptake methanol vapors to convert into <b>3a·2MeOH</b>. The structure of <b>3a</b> is related to that for <b>3a·2MeOH</b> by rotation of complex molecules within the 1D O–H···Cl hydrogen bonding networks and insertion of methanol into it

Synthesis and Crystallographic Studies of Disubstituted Carboranyl Alcohol Derivatives: Prevailing Chiral Recognition?

The syntheses of new <i>o</i>-carboranyldiols bearing aromatic rings bis-[R­(hydroxy)­methyl]-1,2-dicarba-<i>closo</i>-dodecaborane (R = 2-pyridyl <b>1a</b>, 3-pyridyl <b>1b</b>, 4-pyridyl <b>1c</b>, 2-quinolyl <b>1d</b>, 4-quinolyl <b>1e</b>, phenyl <b>1f</b>) are reported. The compounds are obtained as mixtures of meso (<i>syn</i>) and racemic (<i>anti</i>) stereoisomers with a slight diastereomeric excess (<i>syn</i>:<i>anti</i> ratio of 0.7:1) in all cases but in <b>1b</b>. The crystal structures of the meso compounds <i>syn</i><b>-1a</b>·2MeOH, <i>syn</i><b>-1b</b>, <i>syn</i><b>-1f</b>·0.25H₂O and racemic <i>anti</i><b>-1a</b>·MeOH, <i>anti</i><b>-1a</b>·EtOH, and <i>anti</i><b>-1d</b>·2H₂O are reported. We provide an analysis of these compounds by means of NMR and X-ray crystallography, in the context of crystal engineering and chiral recognition. The results show that the crystal packings for these alcohols are dominated by the supramolecular O–H···N and/or O–H···O hydrogen bonds. Supramolecular analysis of all compounds in this work reveals that homochiral self-assembly, that is, formation of homochiral hydrogen bonded complexes, prevails over heterochiral self-assembly (formation of heterochiral hydrogen bonded complexes)

Synthesis and Crystallographic Studies of Disubstituted Carboranyl Alcohol Derivatives: Prevailing Chiral Recognition?

The syntheses of new <i>o</i>-carboranyldiols bearing aromatic rings bis-[R­(hydroxy)­methyl]-1,2-dicarba-<i>closo</i>-dodecaborane (R = 2-pyridyl <b>1a</b>, 3-pyridyl <b>1b</b>, 4-pyridyl <b>1c</b>, 2-quinolyl <b>1d</b>, 4-quinolyl <b>1e</b>, phenyl <b>1f</b>) are reported. The compounds are obtained as mixtures of meso (<i>syn</i>) and racemic (<i>anti</i>) stereoisomers with a slight diastereomeric excess (<i>syn</i>:<i>anti</i> ratio of 0.7:1) in all cases but in <b>1b</b>. The crystal structures of the meso compounds <i>syn</i><b>-1a</b>·2MeOH, <i>syn</i><b>-1b</b>, <i>syn</i><b>-1f</b>·0.25H₂O and racemic <i>anti</i><b>-1a</b>·MeOH, <i>anti</i><b>-1a</b>·EtOH, and <i>anti</i><b>-1d</b>·2H₂O are reported. We provide an analysis of these compounds by means of NMR and X-ray crystallography, in the context of crystal engineering and chiral recognition. The results show that the crystal packings for these alcohols are dominated by the supramolecular O–H···N and/or O–H···O hydrogen bonds. Supramolecular analysis of all compounds in this work reveals that homochiral self-assembly, that is, formation of homochiral hydrogen bonded complexes, prevails over heterochiral self-assembly (formation of heterochiral hydrogen bonded complexes)