Hexene hydrogenation catalysed by the complex monohydrid complexes: A DFT study of associated vs dissociated pathways

Achour, Sofiene; Hosni, Zied; Tangour, Bahoueddine

doi:10.1016/j.jmgm.2020.107583

Cited by 6 publications

(4 citation statements)

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“…[59] Additionally, Grimme's dispersion contribution correction (D3) was added, [60] as previous works have shown that B3LYPÀ D3 scheme provides reliable results for thermochemistry of organometallic compounds. [61][62][63][64][65] The def2SVP basis set, including the ECP for Ru, was employed. [66,67] Due to the key role of solvation in influencing thermodynamic and kinetic parameters, solvent effects were introduced by the polarizable continuum method (PCM).…”

Section: Synthesis Of [Ru((s)-cys)(co)((rr)-skewphos)(phen)]pf 6 (2 R...mentioning

confidence: 99%

Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells

Lovison

Alessi

Allegri

et al. 2022

Chemistry A European J

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The chiral cationic complex [Ru(η1‐OAc)(CO)((R,R)‐Skewphos)(phen)]OAc (2R), isolated from reaction of [Ru(η1‐OAc)(η2‐OAc)(R,R)‐Skewphos)(CO)] (1R) with phen, reacts with NaOPiv and KSAc affording [RuX(CO)((R,R)‐Skewphos)(phen)]Y (X=Y=OPiv 3R; X=SAc, Y=OAc 4R). The corresponding enantiomers 2S‐4S have been obtained from 1S containing (S,S)‐Skewphos. Reaction of 2R and 2S with (S)‐cysteine and NaPF6 at pH=9 gives the diastereoisomers [Ru((S)‐Cys)(CO)(PP)(phen)]PF6 (PP=(R,R)‐Skewphos 2R‐Cys; (S,S)‐Skewphos 2S‐Cys). The DFT energetic profile for 2R with (S)‐cysteine in H2O indicates that aquo and hydroxo species are involved in formation of 2R‐Cys. The stability of the ruthenium complexes in 0.9 % w/v NaCl solution, PBS and complete DMEM medium, as well as their n‐octanol/water partition coefficient (logP), have been evaluated. The chiral complexes show high cytotoxic activity against SW1736, 8505 C, HCT‐116 and A549 cell lines with EC50 values of 2.8–0.04 μM. The (R,R)‐Skewphos derivatives show higher cytotoxicity compared to their enantiomers, 4R (EC50=0.04 μM) being 14 times more cytotoxic than 4S against the anaplastic thyroid cancer 8505 C cell line.

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Section: Synthesis Of [Ru((s)-cys)(co)((rr)-skewphos)(phen)]pf 6 (2 R...mentioning

confidence: 99%

Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells

Lovison

Alessi

Allegri

et al. 2022

Chemistry A European J

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“…1, alkene substrates were modulated by varying the substituents, and phenyl-derived substituents (-Ph-OCH 3 , -Ph, -Ph-NO 2 ) were introduced in Jones's work. 10 Partial atomic charges provide the most widely used model for molecular polarization, and have been used to measure the polarity of double bonds by Truhlar et al 21 Partial atomic charge differences (ACD) between two carbons in C( 1)vC( 2) bonds are computed via the Natural Bond Orbital (NBO) method 22 to measure the degree of bond polarization. The C(2) atoms adjacent to the substituents are suggested to be more positive than the C(1) atoms.…”

Section: Resultsmentioning

confidence: 99%

Is the polarization of the CC bond imperative for bifunctional outer-sphere CC hydrogenation?

et al. 2023

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“…The focus of this theoretical work is to investigate the role of these ligands. Theoretical chemistry plays an increasingly crucial role in understanding reaction mechanisms [47][48][49][50][51][52][53][54], and in some recent cases, new catalysts have been designed theoretically prior to their synthesis [55,56].…”

Section: Introductionmentioning

confidence: 99%

“…The focus of this theoretical work is to investigate the role of these ligands. Theoretical chemistry plays an increasingly crucial role in understanding reaction mechanisms [47–54], and in some recent cases, new catalysts have been designed theoretically prior to their synthesis [55, 56]. This type of study is highly valuable not only for elucidating the reaction mechanism but also for exploring the characteristics of the ligand that undergoes dissociation from the catalyst.…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation of hexene catalyzed by a ruthenium (II) complex with N‐heterocyclic carbene ligands

Achour,

Hosni,

Tangour

2024

Int J of Quantum Chemistry

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In this study, we investigated the mechanism of the inactivated hexene hydrogenation reaction catalyzed by a ruthenium (II) complex containing “N‐heterocyclic carbene” (NHC) ligands, specifically SIMes and CBA, using DFT calculations. Our focus was on RuH(OSO2CF3)(CO)(SIMes)(CBA), which exhibits excellent catalytic behavior. We tested the B3LYP‐D3, cam‐B3LYP, and TPSSh functionals. The hydrogenation reaction is initiated by the release of SIMes rather than CBA due to the lower associated dissociation energy. Our findings indicate a reaction mechanism consisting of two consecutive steps, each involving one hydrogen atom migration. The first step, considered as the kinetically limiting transition state, exhibits a Gibbs free activation barrier of 12.9 kcal mol−1. This step involves two asynchronous processes. The first one describes the migration of the ruthenium hydride to the internal carbon of the olefine function, transitioning from π to σ coordination mode, which promotes the formation of a bond between ruthenium and the terminal olefinic carbon. The second process involves the oxidation of ruthenium from Ru(II) to Ru(IV). This oxidation is crucial as it enables the decomposition of the H2 molecule into two hydrogen atoms bonded to the ruthenium atom. The geometrical structures of the Hidden Reaction Intermediate Ru(II) complex and the quasi‐transition state of the second process have been determined by means of the RIRC technique. The second step entails the migration of one of the newly formed hydrides of the Ru(IV) complex to the terminal olefinic carbon, resulting in the release of hexane with a weak activation Gibbs free energy of .8 kcal mol−1. Lastly, we explored the use of dichloromethane as a solvent, considering the PCM model. The presence of the solvent significantly decreases the energy dissociation of SIMes from 17.9 to 9.0 kcal mol−1, providing notable benefits.

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Hexene hydrogenation catalysed by the complex monohydrid complexes: A DFT study of associated vs dissociated pathways

Cited by 6 publications

References 60 publications

Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells

Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells

Is the polarization of the CC bond imperative for bifunctional outer-sphere CC hydrogenation?

Hydrogenation of hexene catalyzed by a ruthenium (II) complex with N‐heterocyclic carbene ligands

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