Dataset Information

Experimental and DFT studies of sulfadiazine 'piano-stool' Ru(ii) and Rh(iii) complexes.

ABSTRACT: While sulfadiazine (HL^SZ) is extensively used to elaborate complexes of intriguing biological applications (e.g. topical antibiotic silvadene; silver sulfadiazine), the molecular structure modification of sulfadiazine or even other sulfa drugs by coordination to either η⁶-cymene Ru(ii) or η⁵-Cp* Rh(iii) motif has not been investigated. Here, half-sandwich organoruthenium(ii) and organorhodium(iii) compounds of the type [(η⁶-p-cymene)Ru(L^SZ)₂] (1) and [(η⁵-C₅Me₅)Rh(L^SZ)₂] (2) are synthesized, characterized and evaluated for their potential antimicrobial activity. Spectroscopic and single crystal X-ray analysis showed that L^SZ is coordinated to Rh(iii) via both the sulfonamide and pyrimidine nitrogen atoms forming "piano-stool" geometry. In 2, the NMR equivalence clearly pointed to participation of two L^SZ molecules in a fluxional process in which the third bond of the base of the stool is oscillating between two equivalent sulfonamide nitrogen atoms. While 1 was biologically inactive, complex 2 was potent against Gram-positive bacteria, Candida albicans and Cryptococcus neoformans. Hen white egg lysozyme (HEWL), a model protein, reacted covalently with 2via the loss of one L^SZ molecule, while compound 1 decomposed during the interaction with that protein.

SUBMITTER: Mansour AM

PROVIDER: S-EPMC9050370 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Experimental and DFT studies of sulfadiazine 'piano-stool' Ru(ii) and Rh(iii) complexes.

Mansour Ahmed M AM Radacki Krzysztof K

RSC advances 20200312 18

While sulfadiazine (HLSZ) is extensively used to elaborate complexes of intriguing biological applications (e.g. topical antibiotic silvadene; silver sulfadiazine), the molecular structure modification of sulfadiazine or even other sulfa drugs by coordination to either η6-cymene Ru(ii) or η5-Cp* Rh(iii) motif has not been investigated. Here, half-sandwich organoruthenium(ii) and organorhodium(iii) compounds of the type [(η6-p-cymene)Ru(L< ...[more]

PMID: 35492929

Similar Datasets

Project description:We have recently reported a series of piano-stool ruthenium(II) complexes of the general formula [RuCl2(η6-arene)(P(1-pyrenyl)R2R3)] showing excellent cytotoxic activities (particularly when R2 = R3 = methyl). In the present study, new members of this family of compounds have been prepared with the objective to investigate the effect of the steric hindrance of a bulky phosphane ligand, namely diisopropyl(1-pyrenyl)phosphane (L), on exchange reactions involving the coordinated halides (X = Cl, I). Two η6-arene rings were used, i.e. η6-methyl benzoate (mba) and η6-p-cymene (p-cym), and four complexes were synthesized, namely [RuCl2(mba)(L)] (1Cl2iPr), [RuI2(mba)(L)] (1I2iPr), [RuCl2(p-cym)(L)] (2Cl2iPr), and [RuI2(p-cym)(L)] (2I2iPr). Unexpectedly, all of the complexes exhibited poor cytotoxic activities after 24 h of incubation with cells, in contrast to the related compounds previously reported. However, it was observed that aged DMSO solutions of 2I2iPr (from 2 to 7 days) exhibited better activities in comparison to freshly prepared solutions and that the activity improved over "aging" time. Thorough studies were therefore performed to uncover the origin of this lag time in the cytotoxicity efficiency. The data achieved clearly demonstrated that compounds 2I2iPr and 2Cl2iPr were undergoing a series of transformation reactions in DMSO (with higher rates for the iodido complex 2I2iPr), ultimately generating cyclometalated species through a mechanism involving DMSO as a coordinated proton abstractor. The cyclometalated complexes detected in solution were subsequently prepared; hence, pure [RuCl(p-cym)(κ2C-diisopropyl(1-pyrenyl)phosphane)] (3CliPr), [RuI(p-cym)(κ2C-diisopropyl(1-pyrenyl)phosphane)] (3IiPr), and [Ru(p-cym)(κS-dmso)(κ2C-diisopropyl(1-pyrenyl)phosphane)]PF6 (3dmsoiPr) were synthesized and fully characterized. Remarkably, 3CliPr, 3IiPr, and 3dmsoiPr are all very efficient cytotoxic agents, exhibiting slightly better activities in comparison to the chlorido noncyclometalated complexes [RuCl2(η6-arene)(P(1-pyrenyl)R2R3)] described in an earlier report. For comparison purposes, the iodido compounds [RuI2(mba)(dimethyl(1-pyrenyl)phosphane)] (1I2Me) and [RuI2(p-cym)(dimethyl(1-pyrenyl)phosphane)] (2I2Me), bearing the less hindered dimethyl(1-pyrenyl)phosphane ligand, have also been prepared. The cytotoxic and chemical behaviors of 1I2Me and 1I2Me were comparable to those of their chlorido counterparts reported previously.

Project description:The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)3) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)3 (M = Cr, Mo, and W)) complexes. The geometries of (COT)Cr(CO)3 were fully characterized with the PBEPBE, PBE0, B3LYP, and B97-1 functionals with various basis set/ECP combinations, while all investigated (TMCOT)M(CO)3 complexes were fully characterized with the PBEPBE, PBE0, and B3LYP methods. The energetics of the fluxional dynamics of (COT)Cr(CO)3 were examined using the correlation consistent Composite Approach for transition metals (ccCA-TM) to provide reliable energy benchmarks for corresponding DFT results. The PBE0/BS1 results are in semiquantitative agreement with the ccCA-TM results. Various transition states were identified for the fluxional processes of (COT)Cr(CO)3. The PBEPBE/BS1 energetics indicate that the 1,2-shift is the lowest energy fluxional process, while the B3LYP/BS1 energetics (where BS1 = H, C, O: 6-31G(d'); M: mod-LANL2DZ(f)-ECP) indicate the 1,3-shift having a lower electronic energy of activation than the 1,2-shift by 2.9 kcal mol-1. Notably, PBE0/BS1 describes the (CO)3 rotation to be the lowest energy process, followed by the 1,3-shift. Six transition states have been identified in the fluxional processes of each of the (TMCOT)M(CO)3 complexes (except for (TMCOT)W(CO)3), two of which are 1,2-shift transition states. The lowest-energy fluxional process of each (TMCOT)M(CO)3 complex (computed with the PBE0 functional) has a ΔG‡ of 12.6, 12.8, and 13.2 kcal mol-1 for Cr, Mo, and W complexes, respectively. Good agreement was observed between the experimental and computed 1H-NMR and 13C-NMR chemical shifts for (TMCOT)Cr(CO)3 and (TMCOT)Mo(CO)3 at three different temperature regimes, with coalescence of chemically equivalent groups at higher temperatures.

Dataset Information

Experimental and DFT studies of sulfadiazine 'piano-stool' Ru(ii) and Rh(iii) complexes.

Publications

Experimental and DFT studies of sulfadiazine 'piano-stool' Ru(ii) and Rh(iii) complexes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets