Theoretical Chemistry Accounts

, Volume 127, Issue 5–6, pp 539–550 | Cite as

How do phosphoramides compete with phosphine oxides in lanthanide complexation? Structural, electronic and energy aspects at ab initio and DFT levels

  • Khodayar GholivandEmail author
  • Hamid Reza Mahzouni
  • Mehdi D. Esrafili
Regular Article


Novel comparison of the structural, electronic and energy aspects of lanthanide complexes of model phosphoramides (PAs) with those of phosphine oxides (POs), phosphate esters (PEs) and phosphoryl trihalides (PHs) has been carried out by ab initio and DFT calculations. Atoms in Molecules (AIM) and Natural Bonding Orbital (NBO) analyses were performed to understand the electronic structure of ligands L and related complexes, L–Ln3+. NBO analysis indicates that the negative charge on phosphoryl oxygen (OP) and the p character of the phosphoryl lone pair, Lp(OP), increase in the order PH < PE < PO < PA. Positive charge of the lanthanide cation in PA complexes is less than those of PH, PE and PO complexes, due to the more intense ligand to metal charge transfer (LMCT). The metal–ligand distance decreases in the order PH > PE > PO > PA, which is confirmed by the results of AIM analysis. Charge density at the bond critical point of L–Ln3+ follows the sequence PH < PE < PO < PA. The results of the Energy Decomposition Analysis (EDA) indicate that the donative interaction and LMCT increases in order PH < PO < PE < PA. The effect of basis set superposition error (BSSE) on the L···Ln3+ interaction energies was also studied in detail at DFT, MP2 and CCSD(T) levels using the counterpoise (CP) method. Trends in the CP-corrected L–Ln3+ bond energies are in good accordance with the optimized OP···Ln3+ distances. The results show that the difference between CP-corrected and uncorrected interaction energies in PA complexes is larger than those in the others, because PAs are more deformable. It is depicted that PAs are comparable with POs in lanthanide complexation.


Lanthanide complex DFT calculation NBO AIM Phosphoramide BSSE 



Support of this work by Tarbiat Modares University is gratefully acknowledged. We thank also Dr. Afshin Abbasi for his comments and helpful discussions.


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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Khodayar Gholivand
    • 1
    Email author
  • Hamid Reza Mahzouni
    • 1
  • Mehdi D. Esrafili
    • 1
  1. 1.Department of ChemistryTarbiat Modares UniversityTehranIran

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