Chasing the Evasive Fe=O Stretch and the Spin State of the Iron(IV)-Oxo Complexes by Photodissociation Spectroscopy

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F17%3A00471901" target="_blank" >RIV/61388955:_____/17:00471901 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/17:10359781
Result on the web
<a href="http://dx.doi.org/10.1021/jacs.6b12291" target="_blank" >http://dx.doi.org/10.1021/jacs.6b12291</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacs.6b12291" target="_blank" >10.1021/jacs.6b12291</a>

Result language
angličtina
Original language name
Chasing the Evasive Fe=O Stretch and the Spin State of the Iron(IV)-Oxo Complexes by Photodissociation Spectroscopy
Original language description
We demonstrate the application of infrared photodissocation spectroscopy for determination of the Fe=O stretching frequencies of high-valent iron(IV)-oxo complexes [(L)Fe(O)(X)]2+/+ (L = TMC, N4Py, PyTACN, and X = CH3CN, CF3SO3, ClO4, CF3COO, NO3, N3). We show that the values determined by resonance Raman spectroscopy in acetonitrile solutions are on average 9 cm-1 red-shifted with respect to unbiased gas-phase values. Furthermore, we show the assignment of the spin state of the complexes based on the vibrational modes of a coordinated anion and compare reactivities of various iron(IV)-oxo complexes generated as dications or monocations (bearing an anionic ligand). The coordinated anions can drastically affect the reactivity of the complex and should be taken into account when comparing reactivities of complexes bearing different ligands. Comparison of reactivities of [(PyTACN)Fe(O)(X)]+ generated in different spin states and bearing different anionic ligands X revealed that the nature of anion influences the reactivity more than the spin state. The triflate and perchlorate ligands tend to stabilize the quintet state of [(PyTACN)Fe(O)(X)]+, whereas trifluoroacetate and nitrate stabilize the triplet state of the complex.
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry

Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year
2017
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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