Technetium and Rhenium Pentacarbonyl Complexes with C<sub>2</sub> and C<sub>11</sub> ω-Isocyanocarboxylic Acid Esters

Miroslavov, A. E.; Polotskii, Yuriy S.; Gurzhiy, Vladislav V.; Ivanov, А. Yu.; Лумпов, А. А.; Tyupina, M. Yu.; Sidorenko, G. V.; Tolstoy, Peter M.; Maltsev, Daniil A.; Suglobov, D.N.

doi:10.1021/ic500327s

Cited by 18 publications

(13 citation statements)

References 10 publications

(33 reference statements)

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“…Figure illustrates the 99 Tc NMR spectrum of 7 with a Tc–P coupling to the axial PPh 3 ligands of 549 Hz. Such couplings are in accord with those observed in the other few [Tc(L)(CO) 2 (PPh 3 ) 2 ] complexes, where L represents chelating dithioligands. − …”

Section: Results and Discussionsupporting

confidence: 88%

“…Despite the fact that with the development of 99m Tc sestamibi an isonitrile complex of technetium(I) became one of the most used radiopharmaceuticals worldwide, , the fundamental coordination chemistry of technetium with this class of ligands is relatively little explored. Most of the Tc isocyanide complexes contain the metal in low oxidation states. − In a recent report, also the access to corresponding nitrido and phenylimido complexes of technetium(V) is described . The stabilization of high oxidation states became possible by the use of sterically encumbered terphenylisocyanides, which allowed the tuning of bonding properties in a wide range.…”

Section: Results and Discussionmentioning

confidence: 99%

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[Tc(OH₂)(CO)₃(PPh₃)₂]⁺: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

Jungfer

Abram

2021

Inorg. Chem.

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A scalable synthesis of the novel and highly reactive [Tc(OH 2 )(CO) 3 (PPh 3 ) 2 ] + cation is described. The ligandexchange chemistry of this compound with neutral ligands coordinating through C, N, O, S, Se, and Te has been explored systematically. The complexes either retain the original mer-trans tricarbonyl core under exclusive exchange of the aqua ligand or form dicarbonyl complexes by thermal decarbonylation. Ligand exchange reactions starting from [Tc(OH 2 )(CO) 3 (PPh 3 ) 2 ] + proceed under mild conditions and are generally almost quantitative. Some of the formed complexes are remarkably stable and inert, while others provide products with one labile ligand for further reactions. The derived complexes of the type [Tc(L)-(CO) 3 (PPh 3 ) 2 ] + and [Tc(L) 2 (CO) 2 (PPh 3 ) 2 ] + represent an interesting opportunity for the development of 99m Tc complexes with potential use in radiopharmacy. The ready displacement of the aqua ligand highlights the synthetic value of [Tc(OH 2 )(CO) 3 (PPh 3 ) 2 ] + as a reactive entry point for further studies in the little explored field of the organometallic chemistry of technetium.

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Section: Results and Discussionsupporting

confidence: 88%

Section: Results and Discussionmentioning

confidence: 99%

[Tc(OH₂)(CO)₃(PPh₃)₂]⁺: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

Jungfer

Abram

2021

Inorg. Chem.

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“…The synthesis of pentacarbonyltechnetium(I) complexes with one additional isocyanide ligand can readily be performed by a selective exchange of a halide from [Tc(CO) 5 X] species (X = Cl, Br, I). Such reactions are commonly conducted under mild conditions and with the addition of Ag + ions as halide scavengers, 30,31 while heating of the pentacarbonyl halides with an excess of isocyanides results in the formation of neutral tricarbonyl compounds of the composition fac-[Tc(CO) 3 X-(CNR) 2 ]. 32,33 Such facial tricarbonyltechnetium(I) complexes are also obtained during reactions of (NEt 4 ) 2 [Tc(CO) 3 Cl 3 ] or (NBu 4 )[Tc 2 (CO) 6 (μ-Cl) 3 ] (Scheme 1) with alkyl isocyanides.…”

Section: ■ Introductionmentioning

confidence: 99%

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

et al. 2022

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Reactions of the alkyl isocyanide fac-[Tc(CO)3(CNR)2Cl] complexes (2) (CNR = CN n Bu or CN t Bu) with the sterically encumbered isocyanide CNp-FArDarF2 [DArF = 3,5-(CF3)2C6H3] allow a selective exchange of the carbonyl ligands of 2 and the isolation of the mixed-isocyanide complexes mer,trans-[Tc(CNp-FArDarF2)3(CNR)2Cl] (3). Depending on the steric requirements of the residues R, the remaining chlorido ligand can be replaced by another isocyanide ligand. Cationic complexes such as mer-[Tc(CNp-FArDarF2)3(CN n Bu)3]+ (4a) or mer,trans-[Tc(CNp-FArDarF2)3(CN n Bu)2(CN t Bu)]+ (6) have been prepared in this way and isolated as their PF6 – salts. mer,trans-[Tc(CNp-FArDarF2)3(CN n Bu)2(CN t Bu)](PF6) represents to the best of our knowledge the first transition-metal complex with three different isocyanides in its coordination sphere. Since the degree of the ligand exchange seems to be controlled both by the electronic and steric measures of the incoming isocyanides, we undertook similar reactions with the sterically less demanding p-fluorophenyl isocyanide, CNPhpF, which indeed readily led to the hexakis(isocyanide)technetium(I) cation through an exchange of all ligands in the staring materials [Tc2(CO)6(μ-Cl)3]− or fac-[Tc(CO)3(CNR)2Cl]. The influence of the substituents at the isocyanide ligands in such reactions has been reasoned with the density functional theory-derived electrostatic potential at the accessible surface of the corresponding isocyanide carbon atoms.

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“…To estimate the stability of these complexes in a simulated biological medium, we added excess histidine to an aqueous solution of [ 99 Tc(PTA)(CO)5]ClO4. The IR spectra showed that the complex is resistant to "histidine challenge" for at least 24 h. It should be noted that [ 99 Tc(NCR)(CO)5]ClO4 are less stable under these conditions [23]. The CAP complexes are also stable with respect to histidine challenge reaction (Fig.…”

Section: Behavior Of the Pentacarbonyl Phosphine Complexes In Aqueous Solutionsmentioning

confidence: 94%

Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP

Miroslavov

Britvin

Braband

et al. 2019

Journal of Organometallic Chemistry

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Pentacarbonyl complexes of 99Tc and Re [M(CAP)(CO)5]X and [M(PTA)(CO)5]X (M = 99Tc or Re and X = ClO4− or OTf-) with aminophosphine ligands 1,4,7-triaza-9-phosphatricyclo[5.3.214,9]tridecane (CAP) and 1,3,5-triaza-7-phosphaadamantane (PTA) were prepared for the first time by the reaction of [MX(CO)5] (M = 99Tc or Re, X = ClO4− or OTf-) with CAP and PTA in CH2Cl2 at room temperature. The reaction of [TcCl(CO)5] with CAP in refluxing CH2Cl2 yields the tricarbonyl complex [99TcCl(CAP)2(CO)3]. Treatment of [Re(H2O)3(CO)3]Cl with CAP in aqueous solution at 40-50°Cgives the rhenium analog [ReCl(CAP)2(CO)3]. Both penta-and tricarbonyl phosphine complexes were characterized by spectroscopic methods (IR, NMR, MS) and single crystal X-ray diffraction. The [M(PTA)(CO)5]X complexes are soluble in aqueous solutions, whereas their CAP analogs are not. The CAP complexes become water-soluble after acidification with dilute acids. As the pH of their aqueous solutions increases, they start to slowly degrade at pH 8 and completely decompose at pH 14. In acidic media, the pentacarbonyl complexes undergo stepwise protonation and are stable indefinitely.

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Technetium and Rhenium Pentacarbonyl Complexes with C₂ and C₁₁ ω-Isocyanocarboxylic Acid Esters

Cited by 18 publications

References 10 publications

[Tc(OH₂)(CO)₃(PPh₃)₂]⁺: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

[Tc(OH₂)(CO)₃(PPh₃)₂]⁺: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP

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Technetium and Rhenium Pentacarbonyl Complexes with C2 and C11 ω-Isocyanocarboxylic Acid Esters

Cited by 18 publications

References 10 publications

[Tc(OH2)(CO)3(PPh3)2]+: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

[Tc(OH2)(CO)3(PPh3)2]+: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

Mixed-Isocyanide Complexes of Technetium under Steric and Electronic Control

Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP

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Product

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Technetium and Rhenium Pentacarbonyl Complexes with C₂ and C₁₁ ω-Isocyanocarboxylic Acid Esters

[Tc(OH₂)(CO)₃(PPh₃)₂]⁺: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands

[Tc(OH₂)(CO)₃(PPh₃)₂]⁺: A Synthon for Tc(I) Complexes and Its Reactions with Neutral Ligands