A comparison for donor-acceptor interactions between E(PH3)2 and NHEMe ligands (E = C to Pb) of W(CO)5 complexes using energy decomposition analysis method with natural orbitals for chemical valence theory


Authors

  • Huynh Thi Phuong Loan
  • Le Thi Hoa
  • Duong Tuan Quang
  • Tran Duc Sy
  • Dang Tan Hiep
  • Pham Van Tat
  • Nguyen Thi Ai Nhung
DOI: https://doi.org/10.15625/0866-7144.2016-00355

Keywords:

Density functional theory, Bond dissociation energies (BDEs), Energy decomposition analysis (EDA), Natural Orbitals for Chemical Valence (NOCV)

Abstract

Quantum chemical calculations at the BP86/TZ2P+ level of theory are performed for a comparison of density functional theory (DFT) between tetrylones [(CO)5W-{E(PH3)2}] (W5-EP2) and tetrylenes [(CO)5W-{NHEMe}] (W5-NHEMe) when E = C to Pb. The EDA-NOCV results suggest that the W-E bond dissociation energies (BDEs) in tetrylone complexes increase from the lighter to the heavier homologues. The W-E bond dissociation energies (BDEs) trend in W5-EP2 comes from the increase in (CO)5W←E(PH3)2 donation and strong electrostatic attraction, and that the ligands E(PH3)2 (EP2) are strong s-donors and very weak π-donors. The W-E BDEs trend in tetrylene complexes W5-NHEMeis opposite to that of the W5-EP2 complexes which decrease from the lighter to the heavier homologues. The NHEMe ligands are strong s-donors and weak π-acceptors. NOCV pairs were used in a description of the chemical bond between the W(CO)5 fragment and the ligands in the transition-metal complexes and the results indicated that the NOCV pairs lead to very valuable description of the bonding situation of the fragment-ligand bond in complexes.

Keywords. Density functional theory; Bond dissociation energies (BDEs); Energy decomposition analysis (EDA); Natural Orbitals for Chemical Valence (NOCV).

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Published

25-08-2016

How to Cite

Phuong Loan, H. T., Hoa, L. T., Quang, D. T., Sy, T. D., Hiep, D. T., Tat, P. V., & Ai Nhung, N. T. (2016). A comparison for donor-acceptor interactions between E(PH3)2 and NHEMe ligands (E = C to Pb) of W(CO)5 complexes using energy decomposition analysis method with natural orbitals for chemical valence theory. Vietnam Journal of Chemistry, 54(4), 501. https://doi.org/10.15625/0866-7144.2016-00355

Issue

Vol. 54 No. 4 (2016)

Section

Articles