People | Locations | Statistics |
---|---|---|
Ferrari, A. |
| |
Schimpf, Christian |
| |
Dunser, M. |
| |
Thomas, Eric |
| |
Gecse, Zoltan |
| |
Tsrunchev, Peter |
| |
Della Ricca, Giuseppe |
| |
Cios, Grzegorz |
| |
Hohlmann, Marcus |
| |
Dudarev, A. |
| |
Mascagna, V. |
| |
Santimaria, Marco |
| |
Poudyal, Nabin |
| |
Piozzi, Antonella |
| |
Mørtsell, Eva Anne |
| |
Jin, S. |
| |
Noel, Cédric |
| |
Fino, Paolo |
| |
Mailley, Pascal |
| |
Meyer, Ernst |
| |
Zhang, Qi |
| |
Pfattner, Raphael | Brussels |
|
Kooi, Bart J. |
| |
Babuji, Adara |
| |
Pauporte, Thierry |
|
Lu, C.
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (2/2 displayed)
Places of action
article
Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes
Abstract
Previously, we reported the synthesis of Ti[N(o-(NCH2P(Pr-i)(2))C6H4)(3)] and the Fe-Ti complex, FeTi[N(o-(NCH2P(Pr-i)(2) )C6H4)(3)], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc(+)), respectively. Two isostructural redox members, [FeTiL](+) and [FeTiL](-) (2(ox) and 2(red), respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL](+) complex (1(ox)). The solid-state structures of the [FeTiL](+/0/-) series feature short metal-metal bonds, ranging from 1.94-2.38 angstrom, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 angstrom). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and Fe-57 Mossbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL](+,0,-) series are primarily pi-based and that the polarized Fe-Ti pi-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).