Dynamics of Coordinated Phosphonate Group Directly Observed by 17O-NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00586876" target="_blank" >RIV/61388963:_____/24:00586876 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/24:10481689
Result on the web
<a href="https://doi.org/10.1002/chem.202400970" target="_blank" >https://doi.org/10.1002/chem.202400970</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/chem.202400970" target="_blank" >10.1002/chem.202400970</a>
Alternative languages
Result language
angličtina
Original language name
Dynamics of Coordinated Phosphonate Group Directly Observed by 17O-NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue
Original language description
Biological phosphates can coordinate metal ions and their complexes are common in living systems. Dynamics of mutual oxygen atom exchange in the tetrahedral group in complexes has not been investigated. Here, we present a direct experimental proof of exchange (phosphonate rotation) in model Ln(III) complexes of monophosphonate H(4)dota analogue which alters phosphorus atom chirality of coordinated phosphonate monoester. Combination of macrocycle-based isomerism with P-based chirality leads to several diastereoisomers. (Non)-coordinated oxygen atoms were distinguished through O-17-labelled phosphonate group and their mutual exchange was followed by various NMR techniques and DFT calculations. The process is sterically demanding and occurs through bulky bidentate (kappa(2)-PO2)(-) coordination and was observed only in twisted-square antiprism (TSA) diastereoisomer of large Ln(III) ions. Its energy demands increase for smaller Ln(III) ions ((298)Delta G(not equal)(exp./DFT)=51.8/52.1 and 61.0/71.5 kJ mol(-1) for La(III) and Eu(III), respectively). These results are helpful in design of such complexes as MRI CA and for protein paramagnetic NMR probes. It demonstrates usefulness of O-17 NMR to study solution dynamics in complexes involving phosphorus acid derivatives and it may inspire use of this method to study dynamics of phosphoric acid derivatives (as e. g. phosphorus acid-based inhibitors of metalloenzymes) in different areas of chemistry.
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
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA22-34083S" target="_blank" >GA22-34083S: Complexes of fluorinated ligands with paramagnetic metal ions for 19F MRI and bimodal 1H/19F contrast agents</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2024
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemistry - A European Journal
ISSN
0947-6539
e-ISSN
1521-3765
Volume of the periodical
30
Issue of the periodical within the volume
36
Country of publishing house
DE - GERMANY
Number of pages
13
Pages from-to
e202400970
UT code for WoS article
001239455700001
EID of the result in the Scopus database
2-s2.0-85195049395