Bismuth and Lead Hanging‐Carboxylate Porphyrins: An Unexpected Homobimetallic Lead(II) Complex

Halime, Zakaria; Lachkar, Mohammed; Roisnel, Thierry; Furet, Éric; Halet, Jean‐François; Boitrel, Bernard

doi:10.1002/anie.200700543

Cited by 40 publications

(43 citation statements)

References 30 publications

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“…In agreement with this, two Pb-O and three Pb-N bonds are rather long (vide supra). This stereochemically active lone pair of electrons is also consistent with the examination of the deformation electron density map (Figure 9.15) [33].…”

Section: Bis-strapped Porphyrinssupporting

confidence: 70%

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Bismuth Complexes of Porphyrins and their Potential in Medical Applications

Boitrel

2010

Biological Chemistry of Arsenic, Antimony and Bismuth

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In the past, the major medical application of bismuth consisted of the treatment of gastric ulcers by ingestion of large quantities of bismuth citrate. More recently, the resurgence of interest for bismuth medical applications has been more oriented towards possible applications in radiotherapy, and particularly in alpha-radioimmunotherapy (Figure 9.1) [1]. As this specific application will be reviewed exhaustively in Chapter 13 of this book, we will only discuss the design, synthesis and coordination properties of bismuth porphyrin complexes in this chapter, assuming that the goals and limits of this peculiar application are known. However, we should keep in mind that both alpha-emitter isotopes of bismuth-212 and 213 exhibit a very short half life of 60 and 45 min respectively, as this radiochemical property directly implies fast kinetics formation of complexes. Even if this potential application is far from being achieved, this very basic requirement will guide the research for new bismuth porphyrins.From the coordination point of view, porphyrins are known to coordinate most of the metallic and pseudometallic elements, and metalloporphyrins with over 80 different central

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Section: Bis-strapped Porphyrinssupporting

confidence: 70%

“…It has been shown that a correct balance was possible between these two possibilities with exactly the same synthetic pathway applied to the abab conformation, in which the carboxylate group really hangs to the strap (Scheme 9.5) [33].…”

Section: Bis-strapped Porphyrinsmentioning

confidence: 99%

Bismuth Complexes of Porphyrins and their Potential in Medical Applications

Boitrel

2010

Biological Chemistry of Arsenic, Antimony and Bismuth

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“…Such an intramolecular coordination was confirmed by the resolution of the X-ray structure of 5Bi (Fig. 5a) [30]. In this mononuclear complex, the bismuth atom lies 1.31 Å out of the 24-MP where the average value based on known structures is 1.25 Å.…”

Section: Resultsmentioning

confidence: 66%

“…However, the HRMS analysis revealed a 2:1 lead/ porphyrin ratio, and the 1 H NMR spectrum displayed a C 2 symmetry signature. The lead metaloporphyrin crystallized in the monoclinic space group C2/c in a mixture of acetone/water/DMSO [30]. As seen in Fig.…”

Section: Bi(no 3 ) 3 Meoh/pyridinementioning

confidence: 98%

The overhanging carboxylic acid strategy: an alternative route to the porphyrin core expansion/modification for the coordination of large metal ions

Gac

Boitrel

2012

J. Porphyrins Phthalocyanines

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This account summarizes how the binding properties of a regular porphyrin macrocycle for large cations can be significantly modified and even tuned when the surrounding skeleton delivers at least one carboxylic acid group close to the N -core. While kinetics of metal insertion are drastically improved, unique dinuclear species can be obtained with a possible control of the nuclearity. The first incorporation of an α-core emitter radioisotope of particular interest for cancer therapy was recently demonstrated. All in all, this overhanging carboxylic acid strategy can be regarded as an alternative to either expanded porphyrins for the coordination of large cations from groups 14–15 (PbII, BiIII) or contracted and isomeric porphyrins for the coordination of smaller cations from group 12 (HgII)

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“…Furthermore, to significantly increase the number of boron atoms around the porphyrin as previously mentioned, the 3,5-dime tho xyphenyl group may be further used for a dendri meric approach after deprotection of the hydroxy func tions and reaction with 1-bromomethyl-3,5-di me thoxy benzene [18]. Finally, as it has been de mons trated that a strap linked on the meso positions 5 and 15 deli vers a "hanging" carboxylate group to sta bi lize bis muth in the porphyrin [19], we have selec ted por phy rin 15 as the main target of this study.…”

Section: Resultsmentioning

confidence: 98%