Abstract
The edge-bridged open ferrocenes, Fe(dmch)2 (1), Fe(c-C7H9)2 (2), and Fe(c-C8H11)2 (3, dmch = dimethylcyclohexadienyl; c-C7H9 = cycloheptadienyl; c-C8H11 = cyclooctadienyl) are more readily oxidized than ferrocene by ca. 460−680 mV, the ease of oxidation increasing with ring size. The kinetic stabilities of the 17-electron cations follow a trend that is opposite to their thermodynamic ease of formation. ESR measurements show that the cations are low spin, suggesting a mainly Fe(3dz2) SOMO. The cation Fe(dmch)2+ was isolated as a deep green [Fe(dmch)2][B(C6H5)4] salt. Both the neutral and cationic forms of Fe(dmch)2 have been studied by X-ray diffraction, thereby allowing for structural comparisons of the two species. In particular, the oxidation of the 18-electron Fe(dmch)2 complex leads to the adoption of a nearly staggered conformation, similar to what was previously found only for early metals such as titanium and vanadium. As in the case of ferrocene, oxidation is accompanied by an increase in the average Fe−C bond distance.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
