Structure and redox stability of [Au(III)(X^N^X)PR3] complexes (X = C or N) in aqueous solution: The role of phosphine auxiliary ligand

Delgado, Giset Y. Sánchez; Paschoal, Diego; Oliveira, Marcone Augusto Leal de; Santos, Hélio F. Dos

doi:10.1016/j.jinorgbio.2019.110804

Cited by 10 publications

(6 citation statements)

References 33 publications

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“…The results obtained have shown that this analysis can be a useful tool for rationalizing the catalytic features of these systems through the determination of the effects of the structural changes that occur during a reactional process. [ 61,62 ]…”

Section: Resultsmentioning

confidence: 99%

Propene Hydroformylation Reaction Catalyzed by HRh(CO)(BISBI): A Thermodynamic and Kinetic Analysis of the Full Catalytic Cycle

et al. 2020

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In this article, full quantum mechanical calculations at the DFT‐D level were carried out to study the full catalytic cycle for the hydroformylation of propene, catalyzed by the [HRh(CO)(BISBI)] catalyst. All intermediates and transition states along the elementary steps of the whole catalytic cycle were located and properly characterized. The kinetic constants calculated from transition state theory together with the application of the steady‐state approximation were used to build a kinetic model for the hydroformylation reaction. The calculations show that regioselectivity of the reaction is set at the olefin insertion step, with the H2 oxidative addition being the rate‐determining step of the entire cycle, with an activation energy of 26.0 kcal.mol‐1 for the linear pathway. The kinetic model showed that the CO gas acts as an inhibitor of the reaction at high pressure, and depending on the CO partial pressure, the rate of linear product formation is around 4 to 10 times faster. In line with experimental observations, our computational kinetic model indicated that at high CO partial pressures (> 40 atm), the HRh(CO)(BISBI) catalyst decreases its selectivity. Also was predicted from the computational kinetic model, that the reaction rates for both productions of normal and iso‐butanal are less sensitive to effects of H2 partial pressure concerning the observed with the variation of the partial pressure of CO gas.

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Section: Resultsmentioning

confidence: 99%

Propene Hydroformylation Reaction Catalyzed by HRh(CO)(BISBI): A Thermodynamic and Kinetic Analysis of the Full Catalytic Cycle

et al. 2020

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“…The scope of %V Bur parameter covers the whole range of reactions, including hydrogenation, 31,32 oxidation, [33][34][35] crosscoupling reactions, 36 polymerization, 29,37,38 among others.…”

Section: Sı ´Lvia Escayolamentioning

confidence: 99%

%V_Bur index and steric maps: from predictive catalysis to machine learning

Escayola,

Bahri-Laleh,

Poater

2024

Chem. Soc. Rev.

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“…The cyclometalated complexes 35a-35c, 36a-36f, 37a-37c (Figure 17) feature a remarkable redox activity, giving rise to peculiar pathways of protein targeting. Theoretical investigations on the structure and reactivity of such complexes [95][96][97][98] are reported below (vide infra, Section 3.2. Redox stability).…”

Section: Au(iii) Complexes With Cyclometalated Ligandsmentioning

confidence: 99%

“…One of the strategies adopted to control the reactivity of Au(III)-based antitumor complexes towards their biomolecular targets is the use of appropriate ligands. Due to the exceptional stability and lipophilicity, tertiary phosphines are widely utilized in the design of Au(III)-based metallodrugs [97]. In order to investigate the effects of various phosphines onto the redox stability of [Au(III)(CˆNˆC)PR 3 ] + (Figure 17, structure 35b) (CˆNˆC = 2,6-diphenylpyridine, PR 3 = tertiary phosphine) and [Au(III)(NˆNˆN)PR 3 ] 3+ (NˆNˆN = 2,2 :6 ,2"-terpyridine) complexes (structure 35c), a computational study was carried out to estimate the standard reduction potential ε o for Au 3+ /Au + [97].…”

Section: Redox Stabilitymentioning

confidence: 99%

“…Due to the exceptional stability and lipophilicity, tertiary phosphines are widely utilized in the design of Au(III)-based metallodrugs [97]. In order to investigate the effects of various phosphines onto the redox stability of [Au(III)(CˆNˆC)PR 3 ] + (Figure 17, structure 35b) (CˆNˆC = 2,6-diphenylpyridine, PR 3 = tertiary phosphine) and [Au(III)(NˆNˆN)PR 3 ] 3+ (NˆNˆN = 2,2 :6 ,2"-terpyridine) complexes (structure 35c), a computational study was carried out to estimate the standard reduction potential ε o for Au 3+ /Au + [97]. It was found that εo values were negative for structures 35b and positive for structures 35c with varying spreads of 829 and 507 mV, respectively.…”

Section: Redox Stabilitymentioning

confidence: 99%

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Computational Studies of Au(I) and Au(III) Anticancer MetalLodrugs: A Survey

et al. 2021

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Owing to the growing hardware capabilities and the enhancing efficacy of computational methodologies, computational chemistry approaches have constantly become more important in the development of novel anticancer metallodrugs. Besides traditional Pt-based drugs, inorganic and organometallic complexes of other transition metals are showing increasing potential in the treatment of cancer. Among them, Au(I)- and Au(III)-based compounds are promising candidates due to the strong affinity of Au(I) cations to cysteine and selenocysteine side chains of the protein residues and to Au(III) complexes being more labile and prone to the reduction to either Au(I) or Au(0) in the physiological milieu. A correct prediction of metal complexes’ properties and of their bonding interactions with potential ligands requires QM computations, usually at the ab initio or DFT level. However, MM, MD, and docking approaches can also give useful information on their binding site on large biomolecular targets, such as proteins or DNA, provided a careful parametrization of the metal force field is employed. In this review, we provide an overview of the recent computational studies of Au(I) and Au(III) antitumor compounds and of their interactions with biomolecular targets, such as sulfur- and selenium-containing enzymes, like glutathione reductases, glutathione peroxidase, glutathione-S-transferase, cysteine protease, thioredoxin reductase and poly (ADP-ribose) polymerase 1.

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Structure and redox stability of [Au(III)(X^N^X)PR3] complexes (X = C or N) in aqueous solution: The role of phosphine auxiliary ligand

Cited by 10 publications

References 33 publications

Propene Hydroformylation Reaction Catalyzed by HRh(CO)(BISBI): A Thermodynamic and Kinetic Analysis of the Full Catalytic Cycle

Propene Hydroformylation Reaction Catalyzed by HRh(CO)(BISBI): A Thermodynamic and Kinetic Analysis of the Full Catalytic Cycle

%V_Bur index and steric maps: from predictive catalysis to machine learning

Computational Studies of Au(I) and Au(III) Anticancer MetalLodrugs: A Survey

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Structure and redox stability of [Au(III)(X^N^X)PR3] complexes (X = C or N) in aqueous solution: The role of phosphine auxiliary ligand

Cited by 10 publications

References 33 publications

Propene Hydroformylation Reaction Catalyzed by HRh(CO)(BISBI): A Thermodynamic and Kinetic Analysis of the Full Catalytic Cycle

Propene Hydroformylation Reaction Catalyzed by HRh(CO)(BISBI): A Thermodynamic and Kinetic Analysis of the Full Catalytic Cycle

%VBur index and steric maps: from predictive catalysis to machine learning

Computational Studies of Au(I) and Au(III) Anticancer MetalLodrugs: A Survey

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Structure and redox stability of [Au(III)(X^N^X)PR3] complexes (X = C or N) in aqueous solution: The role of phosphine auxiliary ligand

%V_Bur index and steric maps: from predictive catalysis to machine learning