Exploring the Limits of Dative Boratrane Bonding: Iron as a Strong Lewis Base in Low-Valent Non-Heme Iron-Nitrosyl Complexes.

ABSTRACT: We previously reported the synthesis and preliminary characterization of a unique series of low-spin (ls) {FeNO}^8-10 complexes supported by an ambiphilic trisphosphineborane ligand, [Fe(TPB)(NO)]^+/0/-. Herein, we use advanced spectroscopic techniques and density functional theory (DFT) calculations to extract detailed information as to how the bonding changes across the redox series. We find that, in spite of the highly reduced nature of these complexes, they feature an NO⁺ ligand throughout with strong Fe-NO π-backbonding and essentially closed-shell electronic structures of their FeNO units. This is enabled by an Fe-B interaction that is present throughout the series. In particular, the most reduced [Fe(TPB)(NO)]^- complex, an example of a ls-{F

SUBMITTER: Dong HT 

PROVIDER: S-EPMC7640944 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature