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Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

ABSTRACT: As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential ?-perhalogenation of five ReO meso-tris(para-X-phenyl)corroles, Re[TpXPC](O) (X?=?CF3, H, F, CH3, and OCH3), with elemental chlorine and bromine. With Cl2, ?-octachlorinated products Re[Cl8TpXPC](O) were rapidly obtained for X?=?CF3, H, and CH3, but X?=?OCH3 resulted in overchlorination on the meso-aryl groups. Full ?-octabromination proved slower relative to Cu and Ir corroles, but the desired Re[Br8TpXPC](O) products were finally obtained for X?=?H and F after a week at room temperature. For X?=?CH3 and OCH3, these conditions led to undecabrominated products Re[Br11TpXPC](O). Compared to the ?-unsubstituted starting materials, the ?-octahalogenated products were found to exhibit sharp 1H NMR signals at room temperature, indicating that the aryl groups are locked in place by the ?-halogens, and substantially redshifted Soret and Q bands. Single-crystal X-ray structures of Re[Cl8TpCF3PC](O), Re[Cl8TpCH3PC](O), and Re[Br8TpFPC](O) revealed mild saddling for one Cl8 structure and the Br8 structure. These structural variations, however, appear too insignificant to explain the slowness of the ?-octabromination protocols, which seems best attributed to the deactivating influence of the high-valent Re center.

SUBMITTER: Alemayehu AB

PROVIDER: S-EPMC7665048 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

Alemayehu Abraham B AB Einrem Rune F RF McCormick-McPherson Laura J LJ Settineri Nicholas S NS Ghosh Abhik A

Scientific reports 20201112 1

As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β-perhalogenation of five ReO meso-tris(para-X-phenyl)corroles, Re[TpXPC](O) (X = CF3, H, F, CH3, and OCH3), with elemental chlorine and bromine. With Cl2, β-octachlorinated products Re[Cl8TpXPC](O) were rapidly obtained for X = CF3, H, and CH3, but X = OCH3 res ...[more]

PMID: 33184456

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Project description:A pentapeptide macrocyclic ligand, KYCAR (lysyl-tyrosyl-cystyl-alanyl-arginine), has been designed as a potential chelating ligand for SPECT imaging and therapeutic in vivo agents. This study shows the synthesis and characterization of KYCAR complexes containing nonradioactive rhenium, 99mTc, or 188Re. The metal complexes were also biologically evaluated to determine in vivo distribution in healthy mice. The overall goals of this project were (1) to synthesize the Tc/Re pentapeptide complexes, (2) to identify spectroscopic methods for characterization of syn versus anti rhenium peptide complexes, (3) to analyze the ex vivo stability, and (4) to assess the biological properties of the [99mTc]TcO-KYCAR and [188Re]ReO-KYCAR complexes in vivo. Details on these efforts are provided below.MethodsNatRe/99mTc/188ReO-KYCAR complexes were synthesized, and macroscopic species were characterized via HPLC, IR, NMR, and CD. These characterization data were compared to the crystallographic data of ReO-KYC to assist in the assignment of diastereomers and to aid in the determination of the structure of the complex.ResultsThe radiometal complexes were synthesized with high purity (>95%). HPLC, IR, NMR and CD data on the macroscopic natReO-KYCAR complexes confirm the successful complexation as well as the presence of two diastereomers in syn and anticonformations. Tracer level complexes show favorable stabilities ex vivo for 2+ h.ConclusionMacroscopic metal complexes form diastereomers with the KYCAR ligand; however, this phenomenon is not readily observed on the tracer level due to the rapid interconversion. It was determined through pKa measurements that the macroscopic natReO-KYCAR complex is 0 at physiological pH. The [99mTc]TcO-KYCAR is stable in vitro while the [188Re]ReO-KYCAR shows 50% decomposition in PBS and serum. Biologically, the tracer level complexes clear through the hepatobiliary pathway. Some decomposition of both tracers is evident by uptake in the thyroid and stomach.

Dataset Information

Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

Publications

Synthesis and molecular structure of perhalogenated rhenium-oxo corroles.

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