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

[Image: see text] Previously, we reported the synthesis of Ti[N(o-(NCH(2)P((i)Pr)(2))C(6)H(4))(3)] and the Fe–Ti complex, FeTi[N(o-(NCH(2)P((i)Pr)(2))C(6)H(4))(3)], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox famil...

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Autores principales: Moore, James T., Chatterjee, Sudipta, Tarrago, Maxime, Clouston, Laura J., Sproules, Stephen, Bill, Eckhard, Bernales, Varinia, Gagliardi, Laura, Ye, Shengfa, Lancaster, Kyle M., Lu, Connie C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2019
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6727590/
https://www.ncbi.nlm.nih.gov/pubmed/30957996
http://dx.doi.org/10.1021/acs.inorgchem.9b00442
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author Moore, James T.
Chatterjee, Sudipta
Tarrago, Maxime
Clouston, Laura J.
Sproules, Stephen
Bill, Eckhard
Bernales, Varinia
Gagliardi, Laura
Ye, Shengfa
Lancaster, Kyle M.
Lu, Connie C.
author_facet Moore, James T.
Chatterjee, Sudipta
Tarrago, Maxime
Clouston, Laura J.
Sproules, Stephen
Bill, Eckhard
Bernales, Varinia
Gagliardi, Laura
Ye, Shengfa
Lancaster, Kyle M.
Lu, Connie C.
author_sort Moore, James T.
collection PubMed
description [Image: see text] Previously, we reported the synthesis of Ti[N(o-(NCH(2)P((i)Pr)(2))C(6)H(4))(3)] and the Fe–Ti complex, FeTi[N(o-(NCH(2)P((i)Pr)(2))C(6)H(4))(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 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 (57)Fe 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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spelling pubmed-67275902019-09-06 Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes Moore, James T. Chatterjee, Sudipta Tarrago, Maxime Clouston, Laura J. Sproules, Stephen Bill, Eckhard Bernales, Varinia Gagliardi, Laura Ye, Shengfa Lancaster, Kyle M. Lu, Connie C. Inorg Chem [Image: see text] Previously, we reported the synthesis of Ti[N(o-(NCH(2)P((i)Pr)(2))C(6)H(4))(3)] and the Fe–Ti complex, FeTi[N(o-(NCH(2)P((i)Pr)(2))C(6)H(4))(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 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 (57)Fe 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%). American Chemical Society 2019-04-08 2019-05-06 /pmc/articles/PMC6727590/ /pubmed/30957996 http://dx.doi.org/10.1021/acs.inorgchem.9b00442 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Moore, James T.
Chatterjee, Sudipta
Tarrago, Maxime
Clouston, Laura J.
Sproules, Stephen
Bill, Eckhard
Bernales, Varinia
Gagliardi, Laura
Ye, Shengfa
Lancaster, Kyle M.
Lu, Connie C.
Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes
title Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes
title_full Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes
title_fullStr Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes
title_full_unstemmed Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes
title_short Enhanced Fe-Centered Redox Flexibility in Fe–Ti Heterobimetallic Complexes
title_sort enhanced fe-centered redox flexibility in fe–ti heterobimetallic complexes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6727590/
https://www.ncbi.nlm.nih.gov/pubmed/30957996
http://dx.doi.org/10.1021/acs.inorgchem.9b00442
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