Conformational and structural diversity of iridium dimethyl sulfoxide complexes

Abstract

Transition metal complexes containing dimethyl sulfoxide (DMSO) are important precursors in catalysis and metallodrugs. Understanding the solidstate supramolecular structure is crucial for predicting the properties and biological activity of the material. Several crystalline phases of DMSOcoordinated iridium anions with different cations, potassium (1a) and n-butylammonium (1b), were obtained and their structures determined by X-ray crystallography. Compound (1a) is present in two solvatomorphic forms: and ; the form contains disordered solvent water. In addition, the structures exhibit different rotamers of the trans-[IrCl 4 (DMSO) 2 ] À anion with the trans-DMSO ligands being oriented in anti and gauche conformations. In consideration of these various conformers, the effects of the crystallized solvent and intermolecular interactions on the conformational preferences of the anion are discussed. In addition, density functional theory calculations were used to investigate the energies of the anions in the different conformations. It was found that hydrogen bonds between water and the DMSO complex stabilize the gauche conformation which is the least stable form of the trans-DMSO complex. Consequently, by controlling the number of hydrogen-bond donors and acceptors and the amount of water, it may be possible to obtain different solvatomorphs of clinically significant metallodrugs. research papers Acta Cryst. (2017). B73, 1032-1042 Benjamin M. Ridgway et al. Iridium dimethyl sulfoxide complexes 1033 research papers 1040 Benjamin M. Ridgway et al. Iridium dimethyl sulfoxide complexes

Perrhenate and Pertechnetate Complexes of U(IV), Np(IV), and Pu(IV) with Dimethyl Sulfoxide as an O-Donor Ligand

“…The unique properties of dimethyl sulfoxide (DMSO) make it a universal aprotic solvent widely used in research . Being a neutral molecular ligand, DMSO is used in the synthesis of new compounds, including those containing easily hydrolyzable moieties, as precursor to catalysts for various chemical processes, or in pharmaceuticals. − It is not surprising, therefore, that a large body of data has been accumulated on the interaction of DMSO with metals of different groups along with the crystal structures of the corresponding complexes. There seems to be a clear understanding of the preferential coordination mode of the DMSO molecule.…”

First Iridium(IV) Chloride–Dimethyl Sulfoxide Complex [H(dmso)2][IrCl5(dmso-κO)]: Synthesis and Structure along with Novel Polymorph Modifications of [H(dmso)2][trans-IrCl4(dmso-κS)2] and [H(dmso)][trans-IrCl4(dmso-κS)2]

“…To date, a number of iridium­(I) and iridium­(III) chloride–dimethyl sulfoxide complexes are known. In particular, trans - and cis -isomers of [Ir III Cl 4 (dmso) 2 ] − , [ mer -Ir III Cl 3 (dmso) 3 ], [ cis -Ir I Cl 2 (dmso) 2 ] − , and [Ir I Cl­(dmso) 3 ] have been elucidated structurally. − Notwithstanding, no iridium­(IV) chloride–dimethyl sulfoxide complex has been reported so far.…”

Anion‐Directed Conformation Switching and Trigonal Distortion in Hexakis(methylamine)nickel(II) Cations

“…Although the energy differences between probable conformers were subtle, density functional theory (DFT) optimization indicated the most stable conformer has C 1 symmetry in which six methylamine ligands arrange into a helix to minimize steric repulsions. Meanwhile, external stimuli such as solvents [9a] and ions [12] are known to induce conformation switching. Since crystal structure of [Ni(NH 2 CH 3 ) 6 ] 2+ has not been reported, [13] there is lack of experimental evidence that confirms its conformation in the solid‐state.…”