Electronic Structure of Re2(O2CR)4Cl2 Complexes (R = H, CMe3) and Reassignment of the Electronic Absorption Spectrum of Re2(O2CCMe3)4Cl2

Thomas E Shaw; Titel Jurca; Jennifer C Green; Alfred P Sattelberger

doi:10.1021/acsomega.2c07334

Electronic Structure of Re₂(O₂CR)₄Cl₂ Complexes (R = H, CMe₃) and Reassignment of the Electronic Absorption Spectrum of Re₂(O₂CCMe₃)₄Cl₂

ACS Omega. 2022 Dec 15;7(51):48600-48605. doi: 10.1021/acsomega.2c07334. eCollection 2022 Dec 27.

Authors

Thomas E Shaw^{1

2}, Titel Jurca^{1

2}, Jennifer C Green³, Alfred P Sattelberger¹

Affiliations

¹ Department of Chemistry, University of Central Florida, Orlando, Florida32816, United States.
² Renewable Energy and Chemical Transformations (REACT) Cluster, University of Central Florida, Orlando, Florida32816, United States.
³ Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, OxfordOX1 3QR, U.K.

Abstract

Electronic structure calculations on two dinuclear rhenium(III) carboxylate complexes, Re₂(O₂CH)₄Cl₂ and Re₂(O₂CCMe₃)₄Cl₂, are presented and discussed. Allowed electronic transitions for both molecules were calculated using time-dependent density functional theory (TDDFT). The results for the pivalate dimer, Re₂(O₂CCMe₃)₄Cl₂, are compared with previously reported single-crystal polarized absorption spectra obtained by Martin and co-workers (Inorg. Chem.1984, 23, 699-701). Several revisions to the previous spectral assignments are proposed.