Quantum‐chemical calculations on the slippage of cyclopentadienyl and indenyl ligands in the (η³‐dienyl)Ir(PX₃)₃; (X = H, F, Cl, Me) complexes

Abstract

The structure, electronic properties, and the slippage of cyclopentadienyl (Cp) and indenyl (In) ligands in the (η 3 -dienyl)Ir(PX 3 ) 3 ; (X = H, F, Cl, Me) complexes were illustrated using the hybrid density functional MPW1PW91 theory. The characteristics of chemical bond among the [Ir(PX 3 ) 3 ] + and monoanionic dienyl ligands (Cp and In) fragments was surveyed by the energy decomposition analysis (EDA). Charge decomposition analysis (CDA) and extended charge decomposition analysis (ECDA) were utilized to investigate the electron transfer among the fragments in the studying complexes. The correlations among the computed parameters and Tolman cone angles (θ), Tolman's Electronic Parameter (TEP), as well as the Crabtree's DFT Electronic Parameter (CEP) of the phosphine ligands were explained. K E Y W O R D S charge decomposition analysis (CDA), Crabtree's DFT electronic parameter (CEP), energy decomposition analysis (EDA), extended charge decomposition analysis (ECDA), substituent effect, Tolman cone angles (θ), Tolman's electronic parameter (TEP)