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

Huynh Thi Phuong Loan, Le Thi Hoa, Duong Tuan Quang, Tran Duc Sy, Dang Tan Hiep, Pham Van Tat, Nguyen Thi Ai Nhung

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).

Keywords


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

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