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  Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes

Moore, J. T., Chatterjee, S., Tarrago, M. F. X., Clouston, L. J., Sproules, S., Bill, E., et al. (2019). Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes. Inorganic Chemistry, 58(9), 6199-6214. doi:10.1021/acs.inorgchem.9b00442.

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 Creators:
Moore, James T.1, Author
Chatterjee, Sudipta2, Author
Tarrago, Maxime François Xavier3, Author           
Clouston, Laura J.1, Author
Sproules, Stephen4, Author
Bill, Eckhard5, Author           
Bernales, Varinia1, Author
Gagliardi, Laura1, Author
Ye, Shengfa3, Author           
Lancaster, Kyle M.2, Author
Lu, Connie C.1, Author
Affiliations:
1Department of Chemistry, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455-0431, United States, ou_persistent22              
2Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca New York 14853, United States, ou_persistent22              
3Research Group Ye, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541708              
4WestCHEM, School of Chemistry, University of Glasgow, Glasgow G12 8QQ, United Kingdom, ou_persistent22              
5Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023867              

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 Abstract: Previously, we reported the synthesis of Ti[N(o-(NCH2P(iPr)2)C6H4)3] and the Fe–Ti complex, FeTi[N(o-(NCH2P(iPr)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] (2ox and 2red, respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL]+ complex (1ox). The solid-state structures of the [FeTiL]+/0/– series feature short metal–metal bonds, ranging from 1.94–2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57Fe Mössbauer, 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 Fe-based and that the polarized Fe–Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

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Language(s): eng - English
 Dates: 2019-02-142019-04-082019-05-06
 Publication Status: Published in print
 Pages: 16
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.inorgchem.9b00442
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Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 58 (9) Sequence Number: - Start / End Page: 6199 - 6214 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669