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A theoretical study on the coordination behavior of some phosphoryl, carbonyl and sulfoxide derivatives in lanthanide complexation

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Abstract

The selectivity of phosphoryl P(O)R3, sulfoxide S(O)R2, and carbonyl C(O)R2 (R = NH2, CH3, OH, and F) derivatives with lanthanide cations (La3+, Eu3+, Lu3+) was studied by density functional theory calculations. Theoretical approaches were also used to investigate energy and the nature of metal–ligand interaction in the model complexes. Atoms in molecules and natural bond orbital (NBO) analyses were accomplished to understand the electronic structure of ligands, L, and the related complexes, L–Ln3+. NBO analysis demonstrated that the negative charge on phosphoryl, carbonyl, and sulfoxide oxygen (OP, OC, and OS) has maximum and minimum values when the connected –R groups are –NH2 and –F. The metal–ligand distance declines as, –F > –OH > –CH3 > –NH2. Charge density at the bond critical point and on the lanthanide cation in the L–Ln3+ complexes varies in the order –F < –OH < –CH3 < –NH2, due to greater ligand to metal charge transfer, which is well explained by energy decomposition analysis. It was also illustrated that E(2) values of Lp(N) → σ*(Y–N) vary in the order P=O ˃ S=O ˃ C=O and the related values of Lp(N) → σ*(Y=O) change as C=O ˃ S=O ˃ P=O in (NH2)nYO ligands (Y = P, C, and S). Trends in the L–Ln3+ CP–corrected bond energies are in good accordance with the optimized OY⋯Ln distances. It seems that, comparing the three types of ligands studied, NH2–substituted are the better coordination ligands.

Density functional theory (B3LYP) calculations were used to compare structural, electronic and energy aspects of lanthanide (La, Eu, Lu) complexes of phosphine derivatives with those of carbonyls and sulfoxides in which the R– groups connected to the P=O, C=O and S=O are –NH2, –CH3, –OH and –F.

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Acknowledgment

Financial support of this work by Tarbiat Modares University is gratefully acknowledged.

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Author notes

  1. Khodayar Gholivand, Mohammad Kahnouji and Yazdan Maghsoud contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Tarbiat Modares University, Tehran, Iran

    Khodayar Gholivand, Mohammad Kahnouji, Yazdan Maghsoud, Ehsan Masumian & Mahdieh Hosseini

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  1. Khodayar Gholivand
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  2. Mohammad Kahnouji
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  3. Yazdan Maghsoud
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  4. Ehsan Masumian
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Correspondence to Khodayar Gholivand.

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Highlights

1. The selectivity of phosphoryl P(O)R3, sulfoxide S(O)R2, and carbonyl C(O)R2 (with R = NH2, CH3, OH, and F) derivatives to lanthanide cations (La3+, Eu3+, Lu3+) was studied.

2. Atoms in molecules and natural bonding orbital analyses were performed to understand the electronic structure of ligands L and related complexes, results represented the strongest metal−ligand interaction in (NH2)nYO − Ln3+ complexes.

3. Comparison of the optimized structural parameters and estimated L–Ln3+ bond energies have revealed that the (NH2)nYO⋯Ln3+ interactions are stronger than those of Me-, OH- and F-substituted interactions.

4. Bonding analyses of all (Me/NH2/OH/F)2CO–Ln3+, (Me/NH2/OH/F)2SO–Ln3+ and (Me/NH2/OH/F)3PO–Ln3+ complexes were carried out, in terms of energy-decomposition analysis (EDA).

5. EDA data indicate a significant contribution of charge-transfer from ligand to metal of the total attractive forces but the main contribution to ΔEint is from ΔEelstat.

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Gholivand, K., Kahnouji, M., Maghsoud, Y. et al. A theoretical study on the coordination behavior of some phosphoryl, carbonyl and sulfoxide derivatives in lanthanide complexation. J Mol Model 24, 328 (2018). https://doi.org/10.1007/s00894-018-3865-7

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