DFT study on the mechanism for the substitution of F<sup>−</sup>into Al(iii) complexes in aqueous solution

X, Jin; Qian, Zhaosheng; Lu, Bangmei; Bi, Shuping

doi:10.1039/c0dt00594k

Cited by 11 publications

(8 citation statements)

References 73 publications

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“…Seven-coordinate Rh III species are unlikely to form; coupled with the anticipated Coulombic repulsion between [RhCl 6 ] 3– and hydroxide, associative (A) and interchange associative (I A ) mechanisms are considered to be implausible. Moreover, in computational studies − where A, I A , and interchange dissociation (I D ) ligand exchange mechanisms are proposed the incoming ligand is either neutral or is oppositely charged with respect to the complex. In our [RhCl 6 ] 3– and hydroxide system the rate of chloride substitution also depends on the free hydroxide concentration, which implies that I D in addition to a pure dissociation (D) mechanism must also be taken into account.…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic and DFT Study of Rh^III Chloro Complex Transformation in Alkaline Solutions

et al. 2017

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The hydrolysis of [RhCl] in NaOH-water solutions was studied by spectrophotometric methods. The reaction proceeds via successive substitution of chloride with hydroxide to quantitatively form [Rh(OH)]. Ligand substitution kinetics was studied in an aqueous 0.434-1.085 M NaOH matrix in the temperature range 5.5-15.3 °C. Transformation of [RhCl] into [RhCl(OH)] was found to be the rate-determining step with activation parameters of ΔH = 105 ± 4 kJ mol and ΔS= 59 ± 10 J K mol. The coordinated hydroxo ligand(s) induces rapid ligand substitution to form [Rh(OH)]. By simulating ligand substitution as a dissociative mechanism, using density functional theory (DFT), we can now explain the relatively fast and slow kinetics of chloride substitution in basic and acidic matrices, respectively. Moreover, the DFT calculated activation energies corroborated experimental data that the kinetic stereochemical sequence of [RhCl] hydrolysis in an acidic solution proceeds as [RhCl] → [RhCl(HO)] → cis-[RhCl(HO)]. However, DFT calculations predict in a basic solution the trans route of substitution [RhCl] → [RhCl(OH)] → trans-[RhCl(OH)] is kinetically favored.

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Section: Resultsmentioning

confidence: 99%

Spectroscopic and DFT Study of Rh^III Chloro Complex Transformation in Alkaline Solutions

et al. 2017

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“…301 DFT studies on the mechanism of the substitution of fluoride into Al(III) complexes in aqueous solution indicate associative interchange is favoured for [Al(H 2 O) 6 ] 3+ , whereas the preferred mechanism switches to dissociative interchange for [Al(H 2 O) 5 (OH)] 2+ . 302…”

Section: Boronmentioning

confidence: 99%

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

2013

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While most high and medium oxidation state (O.S. ≥ 3) metal and non-metal fluorides and oxide fluorides are strong Lewis acids, exploration of their coordination chemistry with neutral ligands has been limited and mostly non-systematic. This is despite the very different properties conferred on the acceptor centre by the small electronegative fluoride ligands compared to the heavier halides. This article sets out these key differences, discusses possible synthetic routes, the key characterisation techniques, and appropriate bonding models. Current knowledge of the coordination chemistry of d, f and p-block fluorides and oxide fluorides with neutral ligands (with donor atoms drawn from Groups 15 and 16 and including N-heterocyclic carbenes) is then presented and discussed, and the differences in properties compared to complexes containing the heavier halides are illustrated. The emphasis is on work published post 1990, but earlier work is also included as essential background and where no more recent information exists. Attention is drawn to unexplored areas meriting investigation and to possible applications of these complexes.

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“…As an environmentally ubiquitous inorganic anion, F À has influences on such chemical behaviors as structures and reactivity for all kinds of aqueous Al species by strong bonding to aluminum. [9][10][11][12] Therefore, the study of the interactions between F À and K-Al 13 contributes to further understanding the influence of F À on mineral surface reactivity, thereby providing a possibility of unravelling the transformation and transfer of environmental aluminum.…”

Section: Introductionmentioning

confidence: 99%

Effect of fluorine substitution on structures and reactivity of Keggin-Al₁₃in aqueous solution: an exploration of the fluorine substitution mechanism

Jiang

et al. 2014

Phys. Chem. Chem. Phys.

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The structures and reactivity of fluoridated Keggin-aluminum tridecamers (K-Al13) in aqueous solution were studied using density functional theory (DFT) in order to explore the fluorine substitution process and the influence of F(-) on the chemical behavior of Keggin polynuclear Al species. The structures of fluoridated K-Al13 were optimized with the consideration of both explicit and bulk solvent effects. The obtained optimization parameters indicate that the fluorine substitution on distinct sites results in the different structural changes. The consistency between the computational and experimental (19)F and (27)Al NMR chemical shifts validates the suitable computational method for the present clusters. According to the computed energy barriers of water exchange reactions, it was found that the reactivity of η-OH2 decreases as a function of fluorine bridges. The appearance of fluorine bridges does not change the dissociative activated mechanism, but the larger dissociative trend was observed. Combining the present computational results with previous experimental observations, we reasonably put forward the fluorine substitution process and attempt to interpret the experimental phenomenon concerned at the molecular scale and further reveal the mechanism of F(-) promoting dissolution of mineral.

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DFT study on the mechanism for the substitution of F⁻into Al(iii) complexes in aqueous solution

Cited by 11 publications

References 73 publications

Spectroscopic and DFT Study of Rh^III Chloro Complex Transformation in Alkaline Solutions

Spectroscopic and DFT Study of Rh^III Chloro Complex Transformation in Alkaline Solutions

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Effect of fluorine substitution on structures and reactivity of Keggin-Al₁₃in aqueous solution: an exploration of the fluorine substitution mechanism

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DFT study on the mechanism for the substitution of F−into Al(iii) complexes in aqueous solution

Cited by 11 publications

References 73 publications

Spectroscopic and DFT Study of RhIII Chloro Complex Transformation in Alkaline Solutions

Spectroscopic and DFT Study of RhIII Chloro Complex Transformation in Alkaline Solutions

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Effect of fluorine substitution on structures and reactivity of Keggin-Al13in aqueous solution: an exploration of the fluorine substitution mechanism

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DFT study on the mechanism for the substitution of F⁻into Al(iii) complexes in aqueous solution

Spectroscopic and DFT Study of Rh^III Chloro Complex Transformation in Alkaline Solutions

Spectroscopic and DFT Study of Rh^III Chloro Complex Transformation in Alkaline Solutions

Effect of fluorine substitution on structures and reactivity of Keggin-Al₁₃in aqueous solution: an exploration of the fluorine substitution mechanism