Number of the records: 1
Chasing the Evasive Fe=O Stretch and the Spin State of the Iron(IV)-Oxo Complexes by Photodissociation Spectroscopy
- 1.
SYSNO ASEP 0471901 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Chasing the Evasive Fe=O Stretch and the Spin State of the Iron(IV)-Oxo Complexes by Photodissociation Spectroscopy Author(s) Andris, E. (CZ)
Navrátil, R. (CZ)
Jašík, J. (CZ)
Terencio, T. (CZ)
Srnec, Martin (UFCH-W) RID, ORCID
Costas, M. (ES)
Roithová, J. (CZ)Source Title Journal of the American Chemical Society. - : American Chemical Society - ISSN 0002-7863
Roč. 139, č. 7 (2017), s. 2757-2765Number of pages 9 s. Language eng - English Country US - United States Keywords Coordination reactions ; Inorganic compounds ; Ligands Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects GJ15-10279Y GA ČR - Czech Science Foundation (CSF) Institutional support UFCH-W - RVO:61388955 UT WOS 000394829200033 EID SCOPUS 85013469443 DOI 10.1021/jacs.6b12291 Annotation 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2018
Number of the records: 1