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Mössbauer and Nuclear Resonance Vibrational Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage
[Image: see text] Diketiminate-supported iron complexes are capable of cleaving the strong triple bond of N(2) to give a tetra-iron complex with two nitrides (Rodriguez et al., Science, 2011, 334, 780–783). The mechanism of this reaction has been difficult to determine, but a transient green species...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10647920/ https://www.ncbi.nlm.nih.gov/pubmed/37902987 http://dx.doi.org/10.1021/acs.inorgchem.3c02594 |
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author | Wandzilak, Aleksandra Grubel, Katarzyna Skubi, Kazimer L. McWilliams, Sean F. Bessas, Dimitrios Rana, Atanu Hugenbruch, Stefan Dey, Abhishek Holland, Patrick L. DeBeer, Serena |
author_facet | Wandzilak, Aleksandra Grubel, Katarzyna Skubi, Kazimer L. McWilliams, Sean F. Bessas, Dimitrios Rana, Atanu Hugenbruch, Stefan Dey, Abhishek Holland, Patrick L. DeBeer, Serena |
author_sort | Wandzilak, Aleksandra |
collection | PubMed |
description | [Image: see text] Diketiminate-supported iron complexes are capable of cleaving the strong triple bond of N(2) to give a tetra-iron complex with two nitrides (Rodriguez et al., Science, 2011, 334, 780–783). The mechanism of this reaction has been difficult to determine, but a transient green species was observed during the reaction that corresponds to a potential intermediate. Here, we describe studies aiming to identify the characteristics of this intermediate, using a range of spectroscopic techniques, including Mössbauer spectroscopy, electronic absorption spectroscopy, Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and nuclear resonance vibrational spectroscopy (NRVS) complemented by density functional theory (DFT) calculations. We successfully elucidated the nature of the starting iron(II) species and the bis(nitride) species in THF solution, and in each case, THF breaks up the multiiron species. Various observations on the green intermediate species indicate that it has one N(2) per two Fe atoms, has THF associated with it, and has NRVS features indicative of bridging N(2). Computational models with a formally diiron(0)–N(2) core are most consistent with the accumulated data, and on this basis, a mechanism for N(2) splitting is suggested. This work shows the power of combining NRVS, Mössbauer, NMR, and vibrational spectroscopies with computations for revealing the nature of transient iron species during N(2) cleavage. |
format | Online Article Text |
id | pubmed-10647920 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-106479202023-11-15 Mössbauer and Nuclear Resonance Vibrational Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage Wandzilak, Aleksandra Grubel, Katarzyna Skubi, Kazimer L. McWilliams, Sean F. Bessas, Dimitrios Rana, Atanu Hugenbruch, Stefan Dey, Abhishek Holland, Patrick L. DeBeer, Serena Inorg Chem [Image: see text] Diketiminate-supported iron complexes are capable of cleaving the strong triple bond of N(2) to give a tetra-iron complex with two nitrides (Rodriguez et al., Science, 2011, 334, 780–783). The mechanism of this reaction has been difficult to determine, but a transient green species was observed during the reaction that corresponds to a potential intermediate. Here, we describe studies aiming to identify the characteristics of this intermediate, using a range of spectroscopic techniques, including Mössbauer spectroscopy, electronic absorption spectroscopy, Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and nuclear resonance vibrational spectroscopy (NRVS) complemented by density functional theory (DFT) calculations. We successfully elucidated the nature of the starting iron(II) species and the bis(nitride) species in THF solution, and in each case, THF breaks up the multiiron species. Various observations on the green intermediate species indicate that it has one N(2) per two Fe atoms, has THF associated with it, and has NRVS features indicative of bridging N(2). Computational models with a formally diiron(0)–N(2) core are most consistent with the accumulated data, and on this basis, a mechanism for N(2) splitting is suggested. This work shows the power of combining NRVS, Mössbauer, NMR, and vibrational spectroscopies with computations for revealing the nature of transient iron species during N(2) cleavage. American Chemical Society 2023-10-30 /pmc/articles/PMC10647920/ /pubmed/37902987 http://dx.doi.org/10.1021/acs.inorgchem.3c02594 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Wandzilak, Aleksandra Grubel, Katarzyna Skubi, Kazimer L. McWilliams, Sean F. Bessas, Dimitrios Rana, Atanu Hugenbruch, Stefan Dey, Abhishek Holland, Patrick L. DeBeer, Serena Mössbauer and Nuclear Resonance Vibrational Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage |
title | Mössbauer
and Nuclear Resonance Vibrational
Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage |
title_full | Mössbauer
and Nuclear Resonance Vibrational
Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage |
title_fullStr | Mössbauer
and Nuclear Resonance Vibrational
Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage |
title_full_unstemmed | Mössbauer
and Nuclear Resonance Vibrational
Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage |
title_short | Mössbauer
and Nuclear Resonance Vibrational
Spectroscopy Studies of Iron Species Involved in N–N Bond Cleavage |
title_sort | mössbauer
and nuclear resonance vibrational
spectroscopy studies of iron species involved in n–n bond cleavage |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10647920/ https://www.ncbi.nlm.nih.gov/pubmed/37902987 http://dx.doi.org/10.1021/acs.inorgchem.3c02594 |
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