Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides

Geometrically flexible 9-borabicyclo[3.3.1]nonyl units within the secondary coordination sphere enable isolation of high-spin Fe(ii)-dihydrides stabilized by boron–hydride interactions and a rare example of an isolable S = 3/2 reduction product. The borane-capped Fe(ii)-dihydride: (1) rapidly deprot...

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Autores principales: Kiernicki, John J., Shanahan, James P., Zeller, Matthias, Szymczak, Nathaniel K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6553361/
https://www.ncbi.nlm.nih.gov/pubmed/31293738
http://dx.doi.org/10.1039/c9sc00561g
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author Kiernicki, John J.
Shanahan, James P.
Zeller, Matthias
Szymczak, Nathaniel K.
author_facet Kiernicki, John J.
Shanahan, James P.
Zeller, Matthias
Szymczak, Nathaniel K.
author_sort Kiernicki, John J.
collection PubMed
description Geometrically flexible 9-borabicyclo[3.3.1]nonyl units within the secondary coordination sphere enable isolation of high-spin Fe(ii)-dihydrides stabilized by boron–hydride interactions and a rare example of an isolable S = 3/2 reduction product. The borane-capped Fe(ii)-dihydride: (1) rapidly deprotonates E–H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H(2) upon exposure to π-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N(2) reduction in nitrogenase.
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spelling pubmed-65533612019-07-10 Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides Kiernicki, John J. Shanahan, James P. Zeller, Matthias Szymczak, Nathaniel K. Chem Sci Chemistry Geometrically flexible 9-borabicyclo[3.3.1]nonyl units within the secondary coordination sphere enable isolation of high-spin Fe(ii)-dihydrides stabilized by boron–hydride interactions and a rare example of an isolable S = 3/2 reduction product. The borane-capped Fe(ii)-dihydride: (1) rapidly deprotonates E–H (E = N, O, P, S) bonds to afford borane-stabilized Fe adducts and (2) releases H(2) upon exposure to π-acids. The Lewis acids provide an avenue for redox-leveling in analogy to the near constant operating potential for N(2) reduction in nitrogenase. Royal Society of Chemistry 2019-05-07 /pmc/articles/PMC6553361/ /pubmed/31293738 http://dx.doi.org/10.1039/c9sc00561g Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Kiernicki, John J.
Shanahan, James P.
Zeller, Matthias
Szymczak, Nathaniel K.
Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
title Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
title_full Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
title_fullStr Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
title_full_unstemmed Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
title_short Tuning ligand field strength with pendent Lewis acids: access to high spin iron hydrides
title_sort tuning ligand field strength with pendent lewis acids: access to high spin iron hydrides
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6553361/
https://www.ncbi.nlm.nih.gov/pubmed/31293738
http://dx.doi.org/10.1039/c9sc00561g
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