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19 pages, 3048 KiB

Open AccessArticle

Efficient Direct Nitrosylation of α-Diimine Rhenium Tricarbonyl Complexes to Structurally Nearly Identical Higher Charge Congeners Activable towards Photo-CO Release

by Sara Nasiri Sovari, Isabelle Kolly, Kevin Schindler, Youri Cortat, Shing-Chi Liu, Aurelien Crochet, Aleksandar Pavic and Fabio Zobi

Molecules 2021, 26(17), 5302; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26175302 - 31 Aug 2021

Cited by 3 | Viewed by 2856

Abstract

The reaction of rhenium α-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)₂(NO)(N-N)X]⁺ species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the [...] Read more.

The reaction of rhenium α-diimine (N-N) tricarbonyl complexes with nitrosonium tetrafluoroborate yields the corresponding dicarbonyl-nitrosyl [Re(CO)₂(NO)(N-N)X]⁺ species (where X = halide). The complexes, accessible in a single step in good yield, are structurally nearly identical higher charge congeners of the tricarbonyl molecules. Substitution chemistry aimed at the realization of equivalent dicationic species (intended for applications as potential antimicrobial agents), revealed that the reactivity of metal ion in [Re(CO)₂(NO)(N-N)X]⁺ is that of a hard Re acid, probably due to the stronger π-acceptor properties of NO⁺ as compared to those of CO. The metal ion thus shows great affinity for π-basic ligands, which are consequently difficult to replace by, e.g., σ-donor or weak π-acids like pyridine. Attempts of direct nitrosylation of α-diimine fac-[Re(CO)₃]⁺ complexes bearing π-basic OR-type ligands gave the [Re(CO)₂(NO)(N-N)(BF₄)][BF₄] salt as the only product in good yield, featuring a stable Re-FBF₃ bond. The solid state crystal structure of nearly all molecules presented could be elucidated. A fundamental consequence of the chemistry of [Re(CO)₂(NO)(N-N)X]⁺ complexes, it that the same can be photo-activated towards CO release and represent an entirely new class of photoCORMs. Full article

(This article belongs to the Special Issue Chemistry and Applications of Group 7 Metal Complexes)

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15 pages, 1403 KiB

Open AccessArticle

Sorbitol as a Polar Pharmacological Modifier to Enhance the Hydrophilicity of ^99mTc-Tricarbonyl-Based Radiopharmaceuticals

by Carolina Giammei, Theresa Balber, Katarina Benčurová, Jens Cardinale, Neydher Berroterán-Infante, Marie Brandt, Nedra Jouini, Marcus Hacker, Markus Mitterhauser and Thomas L. Mindt

Molecules 2020, 25(11), 2680; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25112680 - 09 Jun 2020

Cited by 2 | Viewed by 2939

Abstract

The organometallic technetium-99m tricarbonyl core, [^99mTc][Tc(CO)₃(H₂O)₃]⁺, is a versatile precursor for the development of radiotracers for single photon emission computed tomography (SPECT). A drawback of the ^99mTc-tricarbonyl core is its lipophilicity, which [...] Read more.

The organometallic technetium-99m tricarbonyl core, [^99mTc][Tc(CO)₃(H₂O)₃]⁺, is a versatile precursor for the development of radiotracers for single photon emission computed tomography (SPECT). A drawback of the ^99mTc-tricarbonyl core is its lipophilicity, which can influence the pharmacokinetic properties of the SPECT imaging probe. Addition of polar pharmacological modifiers to ^99mTc-tricarbonyl conjugates holds the promise to counteract this effect and provide tumor-targeting radiopharmaceuticals with improved hydrophilicities, e.g., resulting in a favorable fast renal excretion in vivo. We applied the “Click-to-Chelate” strategy for the assembly of a novel ^99mTc-tricarbonyl labeled conjugate made of the tumor-targeting, modified bombesin binding sequence [Nle¹⁴]BBN(7–14) and the carbohydrate sorbitol as a polar modifier. The ^99mTc-radiopeptide was evaluated in vitro with PC-3 cells and in Fox-1^nu mice bearing PC-3 xenografts including a direct comparison with a reference conjugate lacking the sorbitol moiety. The glycated ^99mTc-tricarbonyl peptide conjugate exhibited an increased hydrophilicity as well as a retained affinity toward the Gastrin releasing peptide receptor and cell internalization properties. However, there was no significant difference in vivo in terms of pharmacokinetic properties. In particular, the rate and route of excretion was unaltered in comparison to the more lipophilic reference compound. This could be attributed to the intrinsic properties of the peptide and/or its metabolites. We report a novel glycated (sorbitol-containing) alkyne substrate for the “Click-to-Chelate” methodology, which is potentially of general applicability for the development of ^99mTc-tricarbonyl based radiotracers displaying an enhanced hydrophilicity. Full article

(This article belongs to the Special Issue Chemistry and Applications of Group 7 Metal Complexes)

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Review

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25 pages, 5151 KiB

Open AccessEditor’s ChoiceReview

Anticancer and Antibiotic Rhenium Tri- and Dicarbonyl Complexes: Current Research and Future Perspectives

by Kevin Schindler and Fabio Zobi

Molecules 2022, 27(2), 539; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27020539 - 15 Jan 2022

Cited by 30 | Viewed by 3387

Abstract

Organometallic compounds are increasingly recognized as promising anticancer and antibiotic drug candidates. Among the transition metal ions investigated for these purposes, rhenium occupies a special role. Its tri- and dicarbonyl complexes, in particular, attract continuous attention due to their relative ease of preparation, [...] Read more.

Organometallic compounds are increasingly recognized as promising anticancer and antibiotic drug candidates. Among the transition metal ions investigated for these purposes, rhenium occupies a special role. Its tri- and dicarbonyl complexes, in particular, attract continuous attention due to their relative ease of preparation, stability and unique photophysical and luminescent properties that allow the combination of diagnostic and therapeutic purposes, thereby permitting, e.g., molecules to be tracked within cells. In this review, we discuss the anticancer and antibiotic properties of rhenium tri- and dicarbonyl complexes described in the last seven years, mainly in terms of their structural variations and in vitro efficacy. Given the abundant literature available, the focus is initially directed on tricarbonyl complexes of rhenium. Dicarbonyl species of the metal ion, which are slowly gaining momentum, are discussed in the second part in terms of future perspective for the possible developments in the field. Full article

(This article belongs to the Special Issue Chemistry and Applications of Group 7 Metal Complexes)

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