Complexation of Ln3+ lanthanide cations with phosphoryl-containing OPR3 ligands: a quantum-mechanics study

Troxler, L.; Dedieu, Alain; Hutschka, F.; Wipff, Georges

doi:10.1016/s0166-1280(97)00434-x

Cited by 37 publications

(52 citation statements)

References 33 publications

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“…including the 4s, 4p, 4d and 4f electrons in the valence space) showed that the use of large core ECP for our purpose is satisfactory. 13 The H, C, N, O, and P atoms were described by the standard "DZ" Dunning-Hay double-ζ basis set 39 adding one 3d polarization function on the P atom of exponent ζ 3d = 0.37 (DZ-P* basis set). Additional calculations were performed on all L, LM 3ϩ , LMCl 3 , L 2 MCl 3 and LH ϩ species, adding polarization functions on all atoms of L (exponents being ζ 3dC = 0.75, ζ 3dO = 0.85, ζ 3dN = 0.80, ζ 2pH = 0.80), leading to the DZ* basis set.…”

Section: Methodsmentioning

confidence: 99%

“…Thus, optimization of the LM 3ϩ complexes started with optimized dihedrals of the corresponding LMg 2ϩ complexes. Note that for the Me 3 PO complexes, the P-Me distances and the P᎐ ᎐ O ؒ ؒ ؒ M 3ϩ angles were optimized, while in the study of Troxler et al, 13 they were kept rigid.…”

Section: Methodsmentioning

confidence: 99%

“…This value is close to the one found with the Me 3 PO, Et 3 PO and Ph 3 PO ligands. 13 In the ligand series, however, the changes in interaction energies with a given cation are much smaller by comparison. The energy difference between Me 3 PO and (MeO) 3 PO complexes is only about 5 kcal mol Ϫ1 for a given cation.…”

Section: The Charged 1 : 1 Lm 3؉ Complexes: Relative Cation-ligand Bimentioning

confidence: 98%

“…However, in CCl 4 solution, Ph 3 PO interacts less (by 0.3 kcal mol Ϫ1 ) than Me 3 PO with phenol, although Ph 3 PO displays the largest interactions with M 3ϩ lanthanides, due to polarization effects. 13 Polarization plays a minor role in hydrogen bonding interactions. Thus, explicit calculations on cation complexes "in the gas phase" are crucial to investigate intrinsic binding features.…”

Section: Introductionmentioning

confidence: 99%

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Interaction of M3+ lanthanide cations with phosphoryl containing (alkyl)3PO versus (alkyl-O)3PO ligands: steric effects are more important than basicity effects †

Schurhammer

Erhart²,

Troxler

et al. 1999

J. Chem. Soc., Perkin Trans. 2

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The concept of acid-base interactions between metallic cations and putative ligands, widely used in cation coordination and complexation chemistry, is discussed from the analysis of M 3ϩ lanthanide cation binding to phosphoryl ligands in the gas phase. We report quantum mechanical calculations on the effect of alkyl vs. O-alkyl substitution in phosphoryl-containing ligands L interacting with M 3ϩ (La 3ϩ , Eu 3ϩ , Yb 3ϩ ; L = Me 3 PO, Me 2 (MeO)PO, Me(MeO) 2 PO and (MeO) 3 PO). In the charged 1 : 1 LM 3ϩ complexes, O-alkyl substituted ligands yield lower interaction energies than the alkyl substituted ones, in agreement with the calculated gas phase basicities. However, the effect is surprisingly small (about 10 times smaller than the alkyl vs. aryl substituent effect). The comparison of LM 3ϩ with neutral LMCl 3 and L 2 MCl 3 complexes reveals an amplification of O-alkyl vs. alkyl weakening effect, though, due to repulsions between L, the counterions, and the other ligand, and to the softer character of the metal-ligand bond. Thus, in condensed phases where the first coordination shell of the cation is saturated and generally contains neutralizing counterions, the better binding of (alkyl) n PO ligands, compared to (alkyl-O) n PO ones results mostly from "steric" interactions in the first coordination sphere, rather than from the changes in oxygen "basicity". The conclusions are validated by a number of comparisons using polarization functions on the ligand and accounting for correlation effects (MP2 or DFT-B3LYP calculations). They are important in the context of designing efficient ionophores for lanthanide and actinide cations.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: The Charged 1 : 1 Lm 3؉ Complexes: Relative Cation-ligand Bimentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Interaction of M3+ lanthanide cations with phosphoryl containing (alkyl)3PO versus (alkyl-O)3PO ligands: steric effects are more important than basicity effects †

Schurhammer

Erhart²,

Troxler

et al. 1999

J. Chem. Soc., Perkin Trans. 2

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“…Quantum‐mechanical (QM) and classical force‐field (molecular mechanics, MM, and molecular dynamics, MD) calculations are an important source of information on these factors. Our group has undertaken QM studies of lanthanide complexes of organophosphorus ligands with both oxygen and sulfur as binding sites 14. 20 The results show that oxygen binding sites generally yield higher binding energies than sulfur binding sites.…”

Section: Introductionmentioning

confidence: 99%

The Energetic and Structural Effects of Steric Crowding in Phosphate and Dithiophosphinate Complexes of Lanthanide Cations M3+: A Computational Study

Boehme¹,

Wipff²

2001

Chem. Eur. J.

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Metal-ligand binding strength and selectivity result from antagonistic metal-ligand M-L attractions and ligand-ligand L-L repulsions. On the basis of quantum-mechanical (QM) calculations on lanthanide complexes, we show that this interplay determines the binding affinities in the gas phase. In the series of [ML3] complexes (M = La, Eu, and Yb) with negatively charged phosphoryl ligands L- = (MeO)2PO2- and Me2PS2-, the binding energies follow the order Yb3+ > Eu3+ > La3- for a given ligand, and (MeO)2PO2- > Me2PS2- for a given cation. However, adding a neutral LH ligand to [ML3] changes the order to Eu3+ > Yb3+ > La3+ for the oxygen ligand and La3+ > Eu3- > Yb3+ for the sulfur ligand, indicating that steric strain in the first coordination sphere is largest for the smallest cation and for sulfur binding sites. We investigated the question of additional hydration of the [ML3LH] complexes in aqueous solution by molecular dynamics (MD) simulations, using two sets of atomic charges. It was found that pairwise additive potentials overestimate the coordination and hydration numbers of the cations, while adding polarization energy terms for the ligands yields better agreement between QM and MD results and supports the concept of steric strain in the first coordination sphere.

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Modeling of Macrocyclic Ligand Complexes

Comba

Martin

Macrocyclic Chemistry

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Complexation of Ln3+ lanthanide cations with phosphoryl-containing OPR3 ligands: a quantum-mechanics study

Cited by 37 publications

References 33 publications

Interaction of M3+ lanthanide cations with phosphoryl containing (alkyl)3PO versus (alkyl-O)3PO ligands: steric effects are more important than basicity effects †

Interaction of M3+ lanthanide cations with phosphoryl containing (alkyl)3PO versus (alkyl-O)3PO ligands: steric effects are more important than basicity effects †

The Energetic and Structural Effects of Steric Crowding in Phosphate and Dithiophosphinate Complexes of Lanthanide Cations M3+: A Computational Study

Modeling of Macrocyclic Ligand Complexes

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