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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...

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Autores principales: Wandzilak, Aleksandra, Grubel, Katarzyna, Skubi, Kazimer L., McWilliams, Sean F., Bessas, Dimitrios, Rana, Atanu, Hugenbruch, Stefan, Dey, Abhishek, Holland, Patrick L., DeBeer, Serena
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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