Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F21%3A00119015" target="_blank" >RIV/00216224:14740/21:00119015 - isvavai.cz</a>
Alternative codes found
RIV/62156489:43210/21:43920110
Result on the web
<a href="https://doi.org/10.1021/acs.inorgchem.1c00204" target="_blank" >https://doi.org/10.1021/acs.inorgchem.1c00204</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.1c00204" target="_blank" >10.1021/acs.inorgchem.1c00204</a>
Alternative languages
Result language
angličtina
Original language name
Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes
Original language description
Nuclear magnetic resonance (NMR) spectroscopy of paramagnetic molecules provides detailed information about their molecular and electron-spin structure. The paramagnetic NMR spectrum is a very rich source of information about the hyperfine interaction between the atomic nuclei and the unpaired electron density. The Fermi-contact contribution to ligand hyperfine NMR shifts is particularly informative about the nature of the metal−ligand bonding and the structural arrangements of the ligands coordinated to the metal center. In this account, we provide a detailed experimental and theoretical NMR study of compounds of Cr(III) and Cu(II) coordinated with substituted acetylacetonate (acac) ligands in the solid state. For the first time, we report the experimental observation of extremely paramagnetically deshielded 13C NMR resonances for these compounds in the range of 900−1200 ppm. We demonstrate an excellent agreement between the experimental NMR shifts and those calculated using relativistic density-functional theory. Crystal packing is shown to significantly influence the NMR shifts in the solid state, as demonstrated by theoretical calculations of various supramolecular clusters. The resonances are assigned to individual atoms in octahedral Cr(acac)3 and square-planar Cu(acac)2 compounds and interpreted by different electron configurations and magnetizations at the central metal atoms resulting in different spin delocalizations and polarizations of the ligand atoms. Further, effects of substituents on the 13C NMR resonance of the ipso carbon atom reaching almost 700 ppm for Cr(acac)3 compounds are interpreted based on the analysis of Fermi-contact hyperfine contributions.
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
2021
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
60
Issue of the periodical within the volume
13
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
9368-9377
UT code for WoS article
000671099600019
EID of the result in the Scopus database
2-s2.0-85110102989