Crystal and Substituent Effects on Paramagnetic NMR Shifts in
Transition-Metal Complexes

J 2021

Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes

NOVOTNÝ, Jan, Lukáš JEREMIAS, Patrick René NIMAX, Stanislav KOMOROVSKY, Ivo HEINMAA et. al.

Basic information

Original name

Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes

Authors

NOVOTNÝ, Jan (203 Czech Republic, belonging to the institution), Lukáš JEREMIAS (203 Czech Republic, belonging to the institution), Patrick René NIMAX (276 Germany, belonging to the institution), Stanislav KOMOROVSKY (703 Slovakia), Ivo HEINMAA (233 Estonia) and Radek MAREK (203 Czech Republic, guarantor, belonging to the institution)

Edition

Inorganic Chemistry, American Chemical Society, 2021, 0020-1669

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10400 1.4 Chemical sciences

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

DOI: 10.1021/acs.inorgchem.1c00204

Impact factor

Impact factor: 5.436

RIV identification code

RIV/00216224:14740/21:00119015

Organization unit

Central European Institute of Technology

DOI

http://dx.doi.org/10.1021/acs.inorgchem.1c00204

UT WoS

000671099600019

Keywords in English

NMR spectroscopy;paramagnetic NMR;solid-state;transition-metal comples;hyperfine interaction

Abstract

V originále

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.

Links

GA18-05421S, research and development project

Name: Rozvoj paramagnetické NMR spektroskopie pro supramolekulární systémy (Acronym: SUPRAMAG)

Investor: Czech Science Foundation

GA21-06991S, research and development project

Name: Relativistické efekty v paramagnetické NMR spektroskopii (Acronym: RELMAG)

Investor: Czech Science Foundation, Relativistic Effects in Paramagnetic NMR Spectroscopy

LM2018140, research and development project

Name: e-Infrastruktura CZ (Acronym: e-INFRA CZ)

Investor: Ministry of Education, Youth and Sports of the CR

90127, large research infrastructures

Name: CIISB II

Citovat

NOVOTNÝ, Jan, Lukáš JEREMIAS, Patrick René NIMAX, Stanislav KOMOROVSKY, Ivo HEINMAA and Radek MAREK. Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes. Inorganic Chemistry. American Chemical Society, 2021, vol. 60, No 13, p. 9368-9377. ISSN 0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.1c00204.

@article{1776582,
   author = {Novotný, Jan and Jeremias, Lukáš and Nimax, Patrick René and Komorovsky, Stanislav and Heinmaa, Ivo and Marek, Radek},
   article_number = {13},
   doi = {http://dx.doi.org/10.1021/acs.inorgchem.1c00204},
   keywords = {NMR spectroscopy;paramagnetic NMR;solid-state;transition-metal comples;hyperfine interaction},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes},
   url = {https://doi.org/10.1021/acs.inorgchem.1c00204},
   volume = {60},
   year = {2021}
}

TY  - JOUR
ID  - 1776582
AU  - Novotný, Jan - Jeremias, Lukáš - Nimax, Patrick René - Komorovsky, Stanislav - Heinmaa, Ivo - Marek, Radek
PY  - 2021
TI  - Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes
JF  - Inorganic Chemistry
VL  - 60
IS  - 13
SP  - 9368-9377
EP  - 9368-9377
PB  - American Chemical Society
SN  - 00201669
KW  - NMR spectroscopy;paramagnetic NMR;solid-state;transition-metal comples;hyperfine interaction
UR  - https://doi.org/10.1021/acs.inorgchem.1c00204
N2  - 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.
ER  -

NOVOTNÝ, Jan, Lukáš JEREMIAS, Patrick René NIMAX, Stanislav KOMOROVSKY, Ivo HEINMAA and Radek MAREK. Crystal and Substituent Effects on Paramagnetic NMR Shifts in Transition-Metal Complexes. \textit{Inorganic Chemistry}. American Chemical Society, 2021, vol.~60, No~13, p.~9368-9377. ISSN~0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.1c00204.

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