Dynamics of Coordinated Phosphonate Group Directly Observed by 17O-NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/00216208:11310/24:10481689

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Dynamics of Coordinated Phosphonate Group Directly Observed by 17O-NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Dynamics of Coordinated Phosphonate Group Directly Observed by 17O-NMR in Lanthanide(III) Complexes of a Mono(ethyl phosphonate) DOTA Analogue

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA22-34083S" target="_blank" >GA22-34083S: Komplexy fluorovaných ligandů s paramagnetickými ionty kovů pro 19F MRI a bimodální 1H/19F kontrastní látky</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

30

Číslo periodika v rámci svazku

36

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

13

Strana od-do

e202400970

Kód UT WoS článku

001239455700001

EID výsledku v databázi Scopus

2-s2.0-85195049395