A multiconfigurational approach to the electronic structure of electro‐generated species of the Re₂(μ‐Ph₂PCH₂PPh₂)(S₂CNEt₂)₄ complex

Abstract

The nature of ReÀ Re bonding in Re 2 (μ-Ph 2 PCH 2 PPh 2 )(S 2 CNEt 2 ) 4 complex, including its neutral (1 0 ) and two oxidized (1 + and 1 2 + ) species, was explored utilizing state-of-the-art quantum chemical methodologies within density functional theory (DFT) and complete active space self-consistent field (CASSCF). Our results show that the ground state electron configuration of the 1 0 is s 2 p 4 d 2 d *2 with an effective bond order (EBO) of 2.73 computed with CASSCF. The oxidation discloses an electron removal from a metal-based orbital, giving 1 + and 1 2 + with an EBO of 2.71 and 2.64, respectively. The relative similarity in EBO values among neutral and oxidized species suggests that the oxidation processes have almost no effect on the ReÀ Re bond strength even though electrons removal from metal-based orbitals because the electrons that occupied the d components of ReÀ Re bonds in 1 + and 1 2 + localized on the two Re ions, thus, they were excluded from EBO estimation.