New Chlorido(dimethyl sulfoxide)iridium(III) Complexes with N⁶‐Substituted Adenines – Kinetic N(7) versus Thermodynamic N(9) Coordinated Adenine Isomers

Abstract

New chlorido(dimethyl sulfoxide)iridium(III) complexes with N 6 -substituted adenine derivatives: [Ir III Cl 4 (DMSO-κS){H-AdeC x -κN(7)}]·nH 2 O [x = 3, n = 3 for 1; x = 4, n = 0.5 and 3 for 2a and 2b, respectively; x = 5, n = 0 for 3; x = 10, n = 0.33 for 4] and [Ir III Cl 4 (DMSO-κS){H-AdeC x -κN(9)}] [x = 3 for 5; x = 4 for 6, x = 5 for 7; x = 10 for 8] have been synthesized and characterized by spectroscopic techniques and by singlecrystal X-ray diffraction studies (1, 2b and 5). In all cases, iridium shows octahedral geometry and is coordinated to four chlorido ligands and one S atom from dimethyl sulfoxide (DMSO-κS). The coordination sphere of the metal is com-

Ir(2-Phenylpyridine)2(benzene-1,2-dithiolate) Anion as a Diastereoselective Metalloligand and Nucleophile: Stereoelectronic Effect, Spectroscopy, and Computational Study of the Methylated and Aurated Complexes and their Oxygenation Products

“…The OS bond lengths and stretching frequencies (1019 and 1149 cm –1 ) and OSO angle of the coordinated sulfinate in 1b are similar to those of [ IrSO 2 SO 2 ] − (1014 and 1149 cm –1 ) and related metal sulfinates (989–1202 cm –1 ) . The OS distances (1.463(3) and 1.473(3) Å), ν­(OS) (1106 cm –1 ), and OS–CH 3 angles (107.2(2)° and 107.2(2)°) in 2b compare favorably with those in Ir III (dimethyl sulfoxide) complexes such as [IrCl 4 (H-adenine)­(DMSO)] and [IrCl 4 (DMSO) 2 ] − (DMSO = dimethyl sulfoxide) and related ruthenium complexes . The infrared spectrum of 1c displays bands ascribable to vibrations of the OS bonds of the sulfinate (1019 and 1155 cm –1 ) and sulfoxide (1108 cm –1 ).…”

9-Ethyladenine: Mechanochemical Synthesis, Characterization, and DFT Calculations of Novel Cocrystals and Salts

“…The adenine arrangement found in compound 4 constitutes an alternative adenine–adenine self-assembled motif not found in DNA nor RNA (to the authors’ knowledge), although it has been previously described by others and several structures are deposited in the CCDC showing such pattern. − …”

“…although it has been previously described by others 55 and several structures are deposited at the CCDC showing such pattern. [56][57][58][59][60][61][62] 9-Ethyladenine-Fumaric acid (1:1) hydrated salt (5). This salt crystallizes in the monoclinic C2/m space group containing one molecule of 9-ethyladenine, half of a fumaric acid, half of a fumarate and one molecule of water in the asymmetric unit.…”

A relativistic DFT methodology for calculating the structures and NMR chemical shifts of octahedral platinum and iridium complexes

“…827979 and R all = 0.0287 34 and the Ir(III) complex [Ir III Cl 4 (DMSO-kS){H-AdeC 3 -kN(9)}] (designated as IrC3AP), with CCDC no. 771879, and R all = 0.0412, 52 which contain metal-coordination spheres and purine moieties identical to those of PtKIN and IrBAP, respectively. The supramolecular clusters were constructed based on the intermolecular contacts in the crystal packing and resulted in central molecules completely enclosed in a crystal environment.…”