Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F23%3A00130308" target="_blank" >RIV/00216224:14740/23:00130308 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.inorgchem.2c03282" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.2c03282</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.2c03282" target="_blank" >10.1021/acs.inorgchem.2c03282</a>
Alternative languages
Result language
angličtina
Original language name
Nature of NMR Shifts in Paramagnetic Octahedral Ru(III) Complexes with Axial Pyridine-Based Ligands
Original language description
In recent decades, transition-metal coordination compounds have been extensively studied for their antitumor and antimetastatic activities. In this work, we synthesized a set of symmetric and asymmetric Ru(III) and Rh(III) coordination compounds of the general structure (Na+/K+/PPh4+/LH+) [trans-M(III)L(eq)nL(ax)2]- (M = Ru(III) or Rh(III); L(eq) = Cl, n = 4; L(eq) = ox, n = 2; L(ax) = 4-R-pyridine, R = CH3, H, C6H5, COOH, CF3, CN; L(ax) = DMSO-S) and systematically investigated their structure, stability, and NMR properties. 1H and 13C NMR spectra measured at various temperatures were used to break down the total NMR shifts into the orbital (temperature independent) and hyperfine (temperature dependent) contributions. The hyperfine NMR shifts for paramagnetic Ru(III) compounds were analyzed in detail by using relativistic density-functional theory (DFT). The effects of i) the 4-R substituent of pyridine, ii) the axial trans ligand L(ax), and iii) the equatorial ligands L(eq) on the distribution of spin density reflected in the “through-bond” (contact) and the “through-space” (pseudocontact) contributions to the hyperfine NMR shifts of the individual atoms of the pyridine ligands are rationalized. Further, we demonstrate the large effects of the solvent on the hyperfine NMR shifts and discuss our observations in the general context of the paramagnetic NMR spectroscopy of transition-metal complexes.
Czech name
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Czech description
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Classification
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
10400 - Chemical sciences
Result continuities
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)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
1520-510X
Volume of the periodical
62
Issue of the periodical within the volume
8
Country of publishing house
US - UNITED STATES
Number of pages
14
Pages from-to
3381-3394
UT code for WoS article
000935442300001
EID of the result in the Scopus database
2-s2.0-85148004658