The Electronic Structure and Bonding of the First p-Block Paddlewheel Complex, Bi2(trifluoroacetate)4, and Comparison to d-Block Transition Metal Paddlewheel Complexes: A Photoelectron and Density Functional Theory Study

摘要

The photoelectron spectrum and a density functional computational analysis of the first p-block paddlewheel complex, Bi2(tfa)4, where tfa = (O2CCF3)?, are reported. The photoelectron spectrum of Bi2(tfa)4 contains an ionization band between the region of metal-based ionizations and the region of overlapping ligand ionizations that is not seen in the photoelectron spectra of d-block paddlewheel complexes. This additional ionization arises from an a1g symmetry combination of the tfa ligand orbitals that is directed for σ bonding with the metals, and the unusual energy of this ionization follows from the different interaction of this orbital with the valence s and p orbitals of Bi compared to the valence d orbitals of transition metals. There is significant mixing between the Bi–Bi σ bond and this a1g M–L σ orbital. This observation led to a re-examination of the ionization differences between Mo2(tfa)4 and W2(tfa)4, where the metal–metal σ and π ionizations are overlapping for the Mo2 molecule but a separate and sharp σ ionization is observed for the W2 molecule. The coalescing of the σ and π bond ionizations of Mo2(tfa)4 is due to greater ligand orbital character in the Mo–Mo σ bond (～7%) versus the W–W σ bond (～1%).