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Tricarbonyl triazolato Re(i) compounds of pyridylbenzimidazole ligands: spectroscopic and antimicrobial activity evaluation.

ABSTRACT: Catalyst-free [3+2] cycloaddition coupling between [Re _n (N₃) _n (CO)_3n L] (n = 1, L = 1-ethyl-2-(pyridin-2-yl)benzimidazole (L¹) and n = 2, L = 1,1'-(hexane-1,6-diyl)bis[2-(pyridin-2-yl)-1H-benzimidazole] (L²)) and dimethyl acetylene dicarboxylate (DMAD) afforded mono- and binuclear triazolate complexes. Spectroscopic data presented unambiguous evidence for isomerization of the kinetically formed N(1) bound triazolate isomer into the N(2) analogue. The solvatochromism properties were assessed by UV/Vis spectroscopy with the aid of time dependent density functional theory calculations. The free ligands and their tricarbonyl triazolato Re(i) complexes were screened for their potential antimicrobial activity against different bacterial and fungal pathogens.

SUBMITTER: Mansour AM

PROVIDER: S-EPMC9034272 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Tricarbonyl triazolato Re(i) compounds of pyridylbenzimidazole ligands: spectroscopic and antimicrobial activity evaluation.

Mansour Ahmed M AM

RSC advances 20210628 37

Catalyst-free [3+2] cycloaddition coupling between [Re n (N3) n (CO)3n L] (n = 1, L = 1-ethyl-2-(pyridin-2-yl)benzimidazole (L1) and n = 2, L = 1,1'-(hexane-1,6-diyl)bis[2-(pyridin-2-yl)-1H-benzimidazole] (L2)) and dimethyl acetylene dicarboxylate (DMAD) afforded mono- and binuclear triazolate complexes. Spectroscopic data presented unambiguous evidence for isomerization of the kinetically ...[more]

PMID: 35480466

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Project description:The excellent π-accepting azodicarboxylic esters adcOR (R = Et, iPr, tBu, Bn (CH2-C6H5) and Ph) and the piperidinyl amide derivative adcpip were used as bridging chelate ligands in dinuclear Re(CO)3 complexes [{Re(CO)3Cl}2(µ-adcOR)] and [{Re(CO)3Cl}2(µ-adcpip)]. From the adcpip ligand the mononuclear derivatives [Re(CO)3Cl(adcpip)] and [Re(CO)3(PPh3)(µ-adcpip)]Cl were also obtained. Optimised geometries from density functional theory (DFT) calculations show syn and anti isomers for the dinuclear fac-Re(CO)3 complexes at slightly different energies but they were not distinguishable from experimental IR or UV–Vis absorption spectroscopy. The electrochemistry of the adc complexes showed reduction potentials slightly below 0.0 V vs. the ferrocene/ferrocenium couple. Attempts to generate the radicals [{Re(CO)3Cl}2(µ-adcOR)]•− failed as they are inherently unstable, losing very probably first the Cl− coligand and then rapidly cleaving one [Re(CO)3] fragment. Consequently, we found signals in EPR very probably due to mononuclear radical complexes [Re(CO)3(solv)(adc)]•. The underlying Cl−→solvent exchange was modelled for the mononuclear [Re(CO)3Cl(adcpip)] using DFT calculations and showed a markedly enhanced Re-Cl labilisation for the reduced compared with the neutral complex. Both the easy reduction with potentials ranging roughly from −0.2 to −0.1 V for the adc ligands and the low-energy NIR absorptions in the 700 to 850 nm range place the adc ligands with their lowest-lying π* orbital being localised on the azo function, amongst comparable bridging chelate N^N coordinating ligands with low-lying π* orbitals of central azo, tetrazine or pyrazine functions. Comparative (TD)DFT-calculations on the Re(CO)3Cl complexes of the adcpip ligand using the quite established basis set and functionals M06-2X/def2TZVP/LANL2DZ/CPCM(THF) and the more advanced TPSSh/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) for single-point calculations with BP86/def2-TZVP(+def2-ECP for Re)/CPCMC(THF) optimised geometries showed a markedly better agreement of the latter with the experimental XRD, IR and UV–Vis absorption data.

Project description:ESKAPE bacteria are a major cause of multidrug-resistant infections, and new drugs are urgently needed to combat these pathogens. Given the importance of iron in bacterial physiology and pathogenicity, iron uptake and metabolism have become attractive targets for the development of new antibacterial drugs. In this scenario, the FDA-approved iron mimetic metal Gallium [Ga(III)] has been successfully repurposed as an antimicrobial drug. Ga(III) disrupts ferric iron-dependent metabolic pathways, thereby inhibiting microbial growth. This work provides the first comparative assessment of the antibacterial activity of Ga(NO3)3 (GaN), Ga(III)-maltolate (GaM), and Ga(III)-protoporphyrin IX (GaPPIX), belonging to the first-, second- and third-generation of Ga(III) formulations, respectively, on ESKAPE species, including reference strains and multidrug-resistant (MDR) clinical isolates. In addition to the standard culture medium Mueller Hinton broth (MHB), iron-depleted MHB (DMHB) and RPMI-1640 supplemented with 10% human serum (HS) (RPMI-HS) were also included in Ga(III)-susceptibility tests, because of their different nutrient and iron contents. All ESKAPE species were resistant to all Ga(III) compounds in MHB and DMHB (MIC > 32 μM), except Staphylococcus aureus and Acinetobacter baumannii, which were susceptible to GaPPIX. Conversely, the antibacterial activity of GaN and GaM was very evident in RPMI-HS, in which the low iron content and the presence of HS better mimic the in vivo environment. In RPMI-HS about 50% of the strains were sensitive (MIC < 32) to GaN and GaM, both compounds showing a similar spectrum of activity, although GaM was more effective than GaN. In contrast, GaPPIX lost its antibacterial activity in RPMI-HS likely due to the presence of albumin, which binds GaPPIX and counteracts its inhibitory effect. We also demonstrated that the presence of multiple heme-uptake systems strongly influences GaPPIX susceptibility in A. baumannii. Interestingly, GaN and GaM showed only a bacteriostatic effect, whereas GaPPIX exerted a bactericidal activity on susceptible strains. Altogether, our findings raise hope for the future development of Ga(III)-based compounds in the treatment of infections caused by multidrug-resistant ESKAPE pathogens.

Dataset Information

Tricarbonyl triazolato Re(i) compounds of pyridylbenzimidazole ligands: spectroscopic and antimicrobial activity evaluation.

Publications

Tricarbonyl triazolato Re(i) compounds of pyridylbenzimidazole ligands: spectroscopic and antimicrobial activity evaluation.

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