Reactivity of hydride bridges in a high-spin [Fe3(μ-H)3]3+ cluster: reversible H2/CO exchange and Fe–H/B–F bond metathesis†
†Electronic supplementary information (ESI) available: Experimental and theoretical procedures and figures, crystallographic details, and theoretical structures. CCDC 1523783 and 1523784. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05583d
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Abstract

The triiron trihydride complex Fe ₃H ₃ L ( 1) [where L ^3– is a tris(β-diketiminate)cyclophanate] reacts with CO and with BF ₃·OEt ₂ to afford (Fe ^ICO) ₂Fe ^II(μ ₃-H) L ( 2) and Fe ₃F ₃ L ( 3), respectively. Variable-temperature and applied-field Mössbauer spectroscopy support the assignment of two high-spin (HS) iron( i) centers and one HS iron( ii) ion in 2. Preliminary studies support a CO-induced reductive elimination of H ₂ from 1, rather than CO trapping a species from an equilibrium mixture. This complex reacts with H ₂ to regenerate 1 under a dihydrogen atmosphere, which represents a rare example of reversible CO/H ₂ exchange and the first to occur at high-spin metal centers, as well as the first example of a reversible multielectron redox reaction at a designed high-spin metal cluster. The formation of 3 proceeds through a previously unreported net fluoride-for-hydride substitution, and 3 is surprisingly chemically inert to Si–H bonds and points to an unexpectedly large difference between the Fe–F and Fe–H bonds in this high-spin system.

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Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

Hong-Peng Jia, Elsje Alessandra Quadrelli (2014)

Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

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Mechanistic insights into nitrogen fixation by nitrogenase enzymes.

J. B. Varley, Y Wang, K Chan … (2015)

Biological nitrogen fixation by nitrogenase enzymes is a process that activates dinitrogen (N2) one of the most inert molecules in nature, within the confines of a living organism and at ambient conditions. Despite decades of study, there are still no complete explanations as to how this is possible. Here we describe a model of N2 reduction using the Mo-containing nitrogenase (FeMoco) that can explain the reactivity of the active site via a series of electrochemical steps that reversibly unseal a highly reactive Fe edge site. Our model can explain the 8 proton-electron transfers involved in biological ammonia synthesis within the kinetic scheme of Lowe and Thorneley, the obligatory formation of one H2 per N2 reduced, and the behavior of known inhibitors.

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Templated Chromophore Assembly by Dynamic Covalent Bonds

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Author and article information

Journal

Journal ID (nlm-ta): Chem Sci

Journal ID (iso-abbrev): Chem Sci

Title: Chemical Science

Publisher: Royal Society of Chemistry

ISSN (Print): 2041-6520

ISSN (Electronic): 2041-6539

Publication date (Print): 1 May 2017

Publication date (Electronic): 11 April 2017

Volume: 8

Issue: 5

Pages: 4123-4129

Affiliations

[a ] Center for Catalysis , University of Florida , 214 Leigh Hall P.O. Box 117200 , Gainesville , FL 32611 , USA . Email: murray@ 123456chem.ufl.edu

[b ] Department of Chemistry , University of Florida , 214 Leigh Hall P.O. Box 117200 , Gainesville , FL 32611 , USA

[c ] Department of Chemistry and Biochemistry , University of California San Diego , 9500 Gilman Drive, MC 0358 , La Jolla , CA 92093-0358 , USA

[d ] Laboratoire de Chimie de Biologie des Métaux , UMR 5249 , Université Joseph Fourier , Grenoble-1, CNRS-CEA 17 Rue des Martyrs , 38054 Grenoble Cedex 9 , France

Author information

Kevin J. Anderton http://orcid.org/0000-0002-2599-9143

Leslie J. Murray http://orcid.org/0000-0002-1568-958X

Article

Publisher ID: c6sc05583d

DOI: 10.1039/c6sc05583d

PMC ID: 5443887

PubMed ID: 28603601

SO-VID: 94725d47-202c-43cf-a59f-774b50ddd510

License:

This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial 3.0 Unported License ( http://creativecommons.org/licenses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

History

Date received : 21 December 2016

Date accepted : 27 March 2017

Notes

†Electronic supplementary information (ESI) available: Experimental and theoretical procedures and figures, crystallographic details, and theoretical structures. CCDC 1523783 and 1523784. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05583d

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