UZH-Logo

Maintenance Infos

Cyclopentadienyl Chemistry in Water: Synthesis and Properties of Bifunctionalized [(η$^5$-C$_5$H$_3${COOR}$_2$)M(CO)$_3$] (M = Re and $^{99m}$Tc) Complexes


Ursillo, Samer; Can, Daniel; N’Dongo, Harmel W Peindy; Schmutz, Paul; Spingler, Bernhard; Alberto, Roger (2014). Cyclopentadienyl Chemistry in Water: Synthesis and Properties of Bifunctionalized [(η$^5$-C$_5$H$_3${COOR}$_2$)M(CO)$_3$] (M = Re and $^{99m}$Tc) Complexes. Organometallics, 33(23):6945-6952.

Abstract

Complexes of the [(η5-C5H4COOR)M(CO)3] type (M = 99mTc, Re; R = targeting function) are basic bioorganometallic structures with the potential of combining molecular imaging (99mTc) with therapy (cold Re or 186/188Re). So far, the single carboxylate group on the cyclopentadienyl ring (Cp–) limited targeting to one function. The concept of Cp– as a scaffold for attaching biological molecules could be extended substantially with two or more functionalities bound to the Cp– ligand. Accordingly, the rarely studied bis-substituted cyclopentadienyl ligands [C5H3(1,2-COOMe)2]− and [C5H3(1,3-COOMe)2]− were synthesized and their coordination to the fac-{M(CO)3}+ moiety was studied in water. Both ligands are deprotonated at physiological pH and do not undergo Diels–Alder reactions. In water, they react directly with [Re(OH2)3(CO)3]+ to form [(η5-C5H3{1,2-COOMe}2)Re(CO)3] and [(η5-C5H3{1,3-COOMe}2)Re(CO)3]. Controlled hydrolysis at neutral to alkaline pH gives the monoesters and fully hydrolyzed [(η5-C5H3{1,2-COOH}2)Re(CO)3] and [(η5-C5H3{1,3-COOH}2)Re(CO)3]. Thermal treatment leads to decarboxylation and formation of [(η5-C5H4COOH)Re(CO)3]. The corresponding 99mTc homologues are directly accessible under slightly acidic conditions from [99mTcO4]− in high yields. In the presented strategy, the Cp– ring acts as a scaffold for attaching multiple targeting agents or pharmacophores at the same time.

Complexes of the [(η5-C5H4COOR)M(CO)3] type (M = 99mTc, Re; R = targeting function) are basic bioorganometallic structures with the potential of combining molecular imaging (99mTc) with therapy (cold Re or 186/188Re). So far, the single carboxylate group on the cyclopentadienyl ring (Cp–) limited targeting to one function. The concept of Cp– as a scaffold for attaching biological molecules could be extended substantially with two or more functionalities bound to the Cp– ligand. Accordingly, the rarely studied bis-substituted cyclopentadienyl ligands [C5H3(1,2-COOMe)2]− and [C5H3(1,3-COOMe)2]− were synthesized and their coordination to the fac-{M(CO)3}+ moiety was studied in water. Both ligands are deprotonated at physiological pH and do not undergo Diels–Alder reactions. In water, they react directly with [Re(OH2)3(CO)3]+ to form [(η5-C5H3{1,2-COOMe}2)Re(CO)3] and [(η5-C5H3{1,3-COOMe}2)Re(CO)3]. Controlled hydrolysis at neutral to alkaline pH gives the monoesters and fully hydrolyzed [(η5-C5H3{1,2-COOH}2)Re(CO)3] and [(η5-C5H3{1,3-COOH}2)Re(CO)3]. Thermal treatment leads to decarboxylation and formation of [(η5-C5H4COOH)Re(CO)3]. The corresponding 99mTc homologues are directly accessible under slightly acidic conditions from [99mTcO4]− in high yields. In the presented strategy, the Cp– ring acts as a scaffold for attaching multiple targeting agents or pharmacophores at the same time.

Citations

1 citation in Web of Science®
1 citation in Scopus®
Google Scholar™

Altmetrics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2014
Deposited On:20 Feb 2015 10:08
Last Modified:05 Apr 2016 18:56
Publisher:American Chemical Society
ISSN:0276-7333
Publisher DOI:https://doi.org/10.1021/om501029e

Download

Full text not available from this repository.View at publisher

TrendTerms

TrendTerms displays relevant terms of the abstract of this publication and related documents on a map. The terms and their relations were extracted from ZORA using word statistics. Their timelines are taken from ZORA as well. The bubble size of a term is proportional to the number of documents where the term occurs. Red, orange, yellow and green colors are used for terms that occur in the current document; red indicates high interlinkedness of a term with other terms, orange, yellow and green decreasing interlinkedness. Blue is used for terms that have a relation with the terms in this document, but occur in other documents.
You can navigate and zoom the map. Mouse-hovering a term displays its timeline, clicking it yields the associated documents.

Author Collaborations