Rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-decanyloxybenzoate: synthesis, electrochemistry and oxidative addition kinetics

Stuurman, Nomampondomise F.; Buitendach, Blenerhassitt E.; Twigge, Linette; Swarts, Pieter J.; Conradie, Jeanet

doi:10.1039/c7nj05039a

Cited by 8 publications

(10 citation statements)

References 41 publications

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“…3 . The same reaction scheme is obtained for the simplified model as for the full experimental model, see Scheme 1 , that are in agreement with experimental observation of the full model [2] . The free energies involved in the transition states and different reaction products of the simplified and full experimental system are compared in Fig.…”

Section: Data Descriptionsupporting

confidence: 83%

“…The goal is to illustrate that DFT calculations of a simplified model give the same information regarding the reaction scheme and free energy data as for the full model, while it requires much less computational resources to obtain the data. Furthermore the reaction scheme of the simplified model are in agreement with experimental observation of the full model [2] .…”

supporting

confidence: 78%

“…

Fig. 1 DFT BP86-D3 optimized geometry of Rh(I) of the full experimental [ 1 , 2 ] and simplified model. Color code (online version): Rh (dark red), O (red), C (black), H (white), P (orange).…”

Section: Data Descriptionmentioning

confidence: 99%

“…

Fig. 3 Relative BP86-D3 calculated free energies ΔG (kJ mol −1 ) of the different Rh(III)-alkyl and Rh(III)-acyl reaction products of the Rh(I) + CH 3 I reaction for the full experimental model [ 1 , 2 ] and the simplified model. G(Rh(I) + CH 3 I) is taken as zero.…”

Section: Data Descriptionmentioning

confidence: 99%

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Data of the rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-hydroxybenzoate plus iodomethane oxidative addition and follow-up reactions

Conradie

2020

Data in Brief

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Density functional theory (DFT) free energy data and the reaction mechanism of the rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-hydroxybenzoate plus iodomethane reaction are presented. The rhodium(I) reactant is a simplified model of the rhodium(I) of the rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-decanyloxybenzoate plus iodomethane reaction (full model), presented in the related research article “Rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-decanyloxybenzoate: A DFT study of Oxidative Addition and Methyl Migration” [1]. The goal is to illustrate that DFT calculations of a simplified model give the same information regarding the reaction scheme and free energy data as for the full model, while it requires much less computational resources to obtain the data. Furthermore the reaction scheme of the simplified model are in agreement with experimental observation of the full model [2] .

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Section: Data Descriptionsupporting

confidence: 83%

supporting

confidence: 78%

“…

Fig. 1 DFT BP86-D3 optimized geometry of Rh(I) of the full experimental [ 1 , 2 ] and simplified model. Color code (online version): Rh (dark red), O (red), C (black), H (white), P (orange).…”

Section: Data Descriptionmentioning

confidence: 99%

“…

Section: Data Descriptionmentioning

confidence: 99%

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Data of the rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-hydroxybenzoate plus iodomethane oxidative addition and follow-up reactions

Conradie

2020

Data in Brief

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“…Probably the most well-known example of a rhodium process used in the industry is the rhodium catalyzed carbonylation of methanol to produce acetic acid by the Monsanto process [ 8 , 9 , 10 ], where the first organometallic step involves the oxidative addition of methyl iodide to cis -[Rh(CO) 2 I 2 ] − . [Rh(β-diketonato)(CO)(PPh) 3 ] complexes, as model catalysts of the first step of the Monsanto process, are well-studied [ 11 , 12 ]. It is found that more electronegative groups attached to the backbone of the β-diketonato ligand and slowed down the oxidative addition reaction rate of methyl iodide to [Rh(β-diketonato)(CO)(PPh) 3 ] complexes [ 11 ].…”

Section: Introductionmentioning

confidence: 99%

Kinetic Study of the Oxidative Addition Reaction between Methyl Iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] Complexes, Utilizing UV–Vis, IR Spectrophotometry, NMR Spectroscopy and DFT Calculations

Ferreira

Conradie

2022

Molecules

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The oxidative addition of methyl iodide to [Rh(β-diketonato)(CO)(PPh)3] complexes, as modal catalysts of the first step during the Monsanto process, are well-studied. The β-diketonato ligand is a bidentate (BID) ligand that bonds, through two O donor atoms (O,O-BID ligand), to rhodium. Imino-β-diketones are similar to β-diketones, though the donor atoms are N and O, referred to as an N,O-BID ligand. In this study, the oxidative addition of methyl iodide to [Rh(imino-β-diketonato)(CO)(PPh)3] complexes, as observed on UV–Vis spectrophotometry, IR spectrophotometry and NMR spectrometry, are presented. Experimentally, one isomer of [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] and two isomers of [Rh(CH3COCHCNHCH3)(CO)(PPh3)] are observed—in agreement with density functional theory (DFT) calculations. Experimentally the [Rh(CH3COCHCNPhCH3)(CO)(PPh3)] + CH3I reaction proceeds through one reaction step, with a rhodium(III)-alkyl as the final reaction product. However, the [Rh(CH3COCHCNHCH3)(CO)(PPh3)] + CH3I reaction proceeds through two reaction steps, with a rhodium(III)-acyl as the final reaction product. DFT calculations of all the possible reaction products and transition states agree with experimental findings. Due to the smaller electronegativity of N, compared to O, the oxidative addition reaction rate of CH3I to the two [Rh(imino-β-diketonato)(CO)(PPh)3] complexes of this study was 7–11 times faster than the oxidative addition reaction rate of CH3I to [Rh(CH3COCHCOCH3)(CO)(PPh3)].

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Electrochemical and Theoretical Modelled Reduction of β‐Diketone Inspired Chalcones

Izuchukwu Ugwu,

Conradie

2024

ChemistrySelect

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The growing interest in synthesizing electrochemically active organic ligands stems from extensive reports highlighting the applications of redox‐active organic molecules. These molecules play a crucial role in capturing and converting CO2 into valuable organic compounds, including carbonates used as solvents in lithium batteries. In this study, we present an electrochemical investigation of two chalcone derivatives, referred to as (1) and (2). We explored the influence of different solvent systems, specifically acetonitrile and dimethyl sulfoxide, on the reduction potential of these chalcones. The reported chalcone derivatives were characterized using various analytical techniques, including UV/Visible spectroscopy, Fourier Transform Infrared spectroscopy, Proton and Carbon‐13 nuclear magnetic resonance, as well as mass spectrometry. The characterization of the reported chalcones, exhibiting properties of both β‐diketones and 2‐hydroxyphenones, is underscored by a density functional theory (DFT) study of chalcones (1) and (2). This research establishes a correlation between the energies calculated through DFT and the experimental reduction potentials of chalcones (1) and (2), in comparing them with a series of β‐diketones and 2‐hydroxyphenones.

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Rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-decanyloxybenzoate: synthesis, electrochemistry and oxidative addition kinetics

Abstract: The influence of a sterically large ligand (CH3COC(C10H21OC6H4COO)COCH3)−, substituted on complex [Rh(CH3COC(C10H21OC6H4COO)COCH3)(CO)(PPh3)], on the ease of rhodium oxidation, is described.

Cited by 8 publications

References 41 publications

Data of the rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-hydroxybenzoate plus iodomethane oxidative addition and follow-up reactions

Data of the rhodium(triphenylphosphine)carbonyl-2,4-dioxo-3-pentyl-4-hydroxybenzoate plus iodomethane oxidative addition and follow-up reactions

Kinetic Study of the Oxidative Addition Reaction between Methyl Iodide and [Rh(imino-β-diketonato)(CO)(PPh)3] Complexes, Utilizing UV–Vis, IR Spectrophotometry, NMR Spectroscopy and DFT Calculations

Electrochemical and Theoretical Modelled Reduction of β‐Diketone Inspired Chalcones

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