Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F17%3A10370934" target="_blank" >RIV/00216208:11310/17:10370934 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/jacs.7b00429" target="_blank" >https://doi.org/10.1021/jacs.7b00429</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.7b00429" target="_blank" >10.1021/jacs.7b00429</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

Popis výsledku v původním jazyce

Iron complex [Fe-III(N-3)(MePy(2)tacn)](PF6)(2) (1), containing a neutral triazacyclononane-based pentadentate ligand, and a terminally bound azide ligand has been prepared and spectroscopically and structurally characterized. Structural details, magnetic susceptibility data, and Mossbauer spectra demonstrate that 1 has a low-spin (S = 1/2) ferric center. X-ray diffraction analysis of 1 reveals remarkably short Fe-N (1.859 angstrom) and long FeN-N-2 (1.246 angstrom) distances, while the FT-IR spectra show an unusually low N-N stretching frequency (2019 cm(-1)), suggesting that the FeN-N-2 bond is particularly weak. Photolysis of 1 at 470 or 530 nm caused N-2 elimination and generation of a nitrido species that on the basis of Mossbauer, magnetic susceptibility, EPR, and X-ray absorption in conjunction with density functional theory computational analyses is formulated as [Fe-V(N)(MePy(2)tacn)](2+) (2). Results indicate that 2 is a low spin (S = 1/2) iron(V) species, which exhibits a short Fe-N distance (1.64 angstrom), as deduced from extended X-ray absorption fine structure analysis. Compound 2 is only stable at cryogenic (liquid N-2) temperatures, and frozen solutions as well as solid samples decompose rapidly upon warming, producing N-2. However, the high-valent compound could be generated in the gas phase, and its reactivity against olefins, sulfides, and substrates with weak C-H bonds studied. Compound 2 proved to be a powerful two electron oxidant that can add the nitrido ligand to olefin and sulfide sites as well as oxidize cyclohexadiene substrates to benzene in a formal H-2-transfer process. In summary, compound 2 constitutes the first case of an octahedral Fe-V(N) species prepared within a neutral ligand framework and adds to the few examples of Fe-V species that could be spectroscopically and chemically characterized.

Název v anglickém jazyce

Generation, Spectroscopic, and Chemical Characterization of an Octahedral Iron(V)-Nitrido Species with a Neutral Ligand Platform

Popis výsledku anglicky

Iron complex [Fe-III(N-3)(MePy(2)tacn)](PF6)(2) (1), containing a neutral triazacyclononane-based pentadentate ligand, and a terminally bound azide ligand has been prepared and spectroscopically and structurally characterized. Structural details, magnetic susceptibility data, and Mossbauer spectra demonstrate that 1 has a low-spin (S = 1/2) ferric center. X-ray diffraction analysis of 1 reveals remarkably short Fe-N (1.859 angstrom) and long FeN-N-2 (1.246 angstrom) distances, while the FT-IR spectra show an unusually low N-N stretching frequency (2019 cm(-1)), suggesting that the FeN-N-2 bond is particularly weak. Photolysis of 1 at 470 or 530 nm caused N-2 elimination and generation of a nitrido species that on the basis of Mossbauer, magnetic susceptibility, EPR, and X-ray absorption in conjunction with density functional theory computational analyses is formulated as [Fe-V(N)(MePy(2)tacn)](2+) (2). Results indicate that 2 is a low spin (S = 1/2) iron(V) species, which exhibits a short Fe-N distance (1.64 angstrom), as deduced from extended X-ray absorption fine structure analysis. Compound 2 is only stable at cryogenic (liquid N-2) temperatures, and frozen solutions as well as solid samples decompose rapidly upon warming, producing N-2. However, the high-valent compound could be generated in the gas phase, and its reactivity against olefins, sulfides, and substrates with weak C-H bonds studied. Compound 2 proved to be a powerful two electron oxidant that can add the nitrido ligand to olefin and sulfide sites as well as oxidize cyclohexadiene substrates to benzene in a formal H-2-transfer process. In summary, compound 2 constitutes the first case of an octahedral Fe-V(N) species prepared within a neutral ligand framework and adds to the few examples of Fe-V species that could be spectroscopically and chemically characterized.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA14-20077S" target="_blank" >GA14-20077S: Nehemové železné katalyzátory: výzkum reakčních mechanismů</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

—

Svazek periodika

139

Číslo periodika v rámci svazku

27

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

9168-9177

Kód UT WoS článku

000405642400020

EID výsledku v databázi Scopus

2-s2.0-85024100976