Reactions of Rh₂(CH₃COO)₄ with thiols and thiolates: a structural study.

ABSTRACT: The structural differences between the aerobic reaction products of Rh₂(AcO)₄ (1; AcO^- = CH₃COO^-) with thiols and thiolates in non-aqueous media are probed by X-ray absorption spectroscopy. For this study, ethanethiol, dihydrolipoic acid (DHLA; a dithiol) and their sodium thiolate salts were used. Coordination of simple thiols to the axial positions of Rh₂(AcO)₄ with Rh-SH bonds of 2.5-2.6 Å keeps the Rh^II-Rh^II bond intact (2.41 ± 0.02 Å) but leads to a colour change from emerald green to burgundy. Time-dependent density functional theory (TD-DFT) calculations were performed to explain the observed shifts in the electronic (UV-vis) absorption spectra. The corresponding sodium thiolates, howev

SUBMITTER: Enriquez Garcia A 

PROVIDER: S-EPMC6412178 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature