Structure and property of complexes of group 13 diyl containing subvalent silylone using energy decomposition analysis with natural orbitals for chemical valence

Abstract

AbstractThe structures and chemical bond in complexes containing subvalent silylone of group 13 diyl W(CO)5‐Si(XCp*)2 (W5‐SiX) with X = B – Tl using energy decomposition analysis (EDA) method combined with natural orbitals for chemical valence (NOCV) theory have been examined with gradient‐corrected DFT at the level BP86/TZ2P+. The calculated equilibrium structures of complexes exhibited that the Si(XCp*)2 ligands are bonded in a tilted orientation to the metal fragment W(CO)5. The EDA‐NOCV results indicated that the Si(XCp*)2 ligands in the complexes are mainly strong σ‐ and weak π‐donors. The trend of the W‐Si bond strength resulted from the increase in the ligand‐metal donation (CO)5W ← Si(XCp*)2. The silylone complexes in this study are suitable targets for synthesis.