f-Element Complexes

Boucekkine, Abdou; Belkhiri, Lotfi

doi:10.1016/b978-0-08-097774-4.00910-4

Cited by 6 publications

(9 citation statements)

References 348 publications

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“…Organoactinide complexes often present structural arrangements and a particular reactivity not noticed in coordination chemistry of transition metals [1][2][3][4][5][6][7]. The knowledge of the Electron Affinities (EA) and Ionization Energies (IE) of organoactinide complexes is essential for the understanding of the redox properties of these species, especially as actinides can exhibit various oxidation states.…”

Section: Introductionmentioning

confidence: 99%

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

et al. 2014

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Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X = F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) = 0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) = 0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) < IE(Cl) < IE(Br) < IE(I) is also well rationalized considering the frontier MO diagrams of these species. Finally, this work confirms the relevance of the Hirshfeld charges analysis which bring to light an excellent linear correlation (R(2) = 0.999) between the variations of the uranium charges and E1/2 in the reduction process of the U(V) species.

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Section: Introductionmentioning

confidence: 99%

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

et al. 2014

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“…The M‐C bond length was longer (0.1–0.2 Å) in complexes with palladium or platinum than those with nickel (Tables . In palladium complexes, this bond length was slightly longer (0.01–0.03 Å) than those in platinum complexes, presumably due to the larger ionic radius of Pd 2+ as compared to Pt 2+ . This disordered trend was also present when comparing the linearity of the P‐M‐P bond angles across the metals, where platinum complexes had bond angles 2–3° less than those in nickel complexes, and palladium complexes had bond angles 2–3° less than platinum complexes.…”

Section: Structural Analysismentioning

confidence: 99%

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

Ellis

Downey

2016

Int J of Quantum Chemistry

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New group 10 metalloorganic complexes are proposed as the basis of new catalysts for the formation of carbon‐phosphorous bonds. Density functional theory (DFT) is applied, using multiple DFT functionals, to model molecular geometry as well as electron density distribution in the highest occupied molecular orbitals (HOMOs) expected to carry out a reductive catalytic cycle. DFT/M06 analysis predicts a robust planar geometry, regardless of alteration of major components. Precursors for rapid catalyst generation should begin with an electron‐withdrawing monodentate ligand. Palladium and platinum catalysts have lower chemical hardness, but the electron distribution in the HOMO of the nickel‐based catalyst is preferred for reductive catalytic mechanisms. Both electron density and chemical hardness, however, are affected by the choice of metal ion and the composition of the monodentate ligand bound to it. Group 10 metalloorganic complexes are modeled as precursors for generating new catalysts for a minimally wasteful method of forming bonds commonly found in biochemically active compounds. Suitable precursors have an accessible metal center, as well as significant the HOMO/LUMO involvement at the metal center. All complexes studied offer similar geometries, but precursor transformation into catalyst depends on the electron‐withdrawing ligand being exchanged. Catalyst turn over number is predicted to depend primarily on the central metal. © 2016 Wiley Periodicals, Inc.

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“…At the dawn of the 21st century, the redox chemistry of organoactinide complexes has experienced a remarkable revival and growth both experimentally and theoretically. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Indeed, in addition to the usual ligands such as chloride, carbocyclic ligands (C 5 R 5 , C 7 H 7 , C 8 H 8 ) and amides NR 2 , the use of a wider range of functionalized groups have led to high oxidation states actinide compounds (> +3) exploiting the stabilization induced by metal-ligand multiple bonds. 17,18 Furthermore, contrarily to the 4f lanthanide electrons which are essentially core electrons, 19 the 5f actinide electrons are involved in the bonding.…”

Section: Introductionmentioning

confidence: 99%

How the Ancillary Ligand X Drives the Redox Properties of Biscyclopentadienyl Pentavalent Uranium Cp₂U(═N–Ar)X Complexes

et al. 2021

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HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

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f-Element Complexes

Cited by 6 publications

References 348 publications

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

How the Ancillary Ligand X Drives the Redox Properties of Biscyclopentadienyl Pentavalent Uranium Cp₂U(═N–Ar)X Complexes

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f-Element Complexes

Cited by 6 publications

References 348 publications

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

How the Ancillary Ligand X Drives the Redox Properties of Biscyclopentadienyl Pentavalent Uranium Cp2U(═N–Ar)X Complexes

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How the Ancillary Ligand X Drives the Redox Properties of Biscyclopentadienyl Pentavalent Uranium Cp₂U(═N–Ar)X Complexes