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

Alexander E. Miroslavov, Sergey N. Britvin, Henrik Braband, Roger Alberto, Ekaterina S. Stepanova, Anna P. Shevyakova, Georgy V. Sidorenko, Alexander A. Lumpov

Research output

Abstract

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 °C gives 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.

Original languageEnglish
Pages (from-to)83-89
Number of pages7
JournalJournal of Organometallic Chemistry
Volume896
DOIs
Publication statusPublished - 15 Sep 2019

Fingerprint

Adamantane
Carbon Monoxide
aqueous solutions
Water
analogs
water
Rhenium
Acidification
Protonation
rhenium
phosphine
phosphines
Ligands
Nuclear magnetic resonance
Single crystals
X ray diffraction
nuclear magnetic resonance
ligands
acids
Acids

Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Miroslavov, Alexander E. ; Britvin, Sergey N. ; Braband, Henrik ; Alberto, Roger ; Stepanova, Ekaterina S. ; Shevyakova, Anna P. ; Sidorenko, Georgy V. ; Lumpov, Alexander A. / Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP. In: Journal of Organometallic Chemistry. 2019 ; Vol. 896. pp. 83-89.
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title = "Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP",
abstract = "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 °C gives 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.",
keywords = "1,3,5-Triaza-7-phosphaadamantane, 1,4,7-Triaza-9-phosphatricyclo[5.3.2]tridecane, Pentacarbonyl complexes, Rhenium, Technetium",
author = "Miroslavov, {Alexander E.} and Britvin, {Sergey N.} and Henrik Braband and Roger Alberto and Stepanova, {Ekaterina S.} and Shevyakova, {Anna P.} and Sidorenko, {Georgy V.} and Lumpov, {Alexander A.}",
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Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP. / Miroslavov, Alexander E.; Britvin, Sergey N.; Braband, Henrik; Alberto, Roger; Stepanova, Ekaterina S.; Shevyakova, Anna P.; Sidorenko, Georgy V.; Lumpov, Alexander A.

In: Journal of Organometallic Chemistry, Vol. 896, 15.09.2019, p. 83-89.

Research output

TY - JOUR

T1 - Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP

AU - Miroslavov, Alexander E.

AU - Britvin, Sergey N.

AU - Braband, Henrik

AU - Alberto, Roger

AU - Stepanova, Ekaterina S.

AU - Shevyakova, Anna P.

AU - Sidorenko, Georgy V.

AU - Lumpov, Alexander A.

PY - 2019/9/15

Y1 - 2019/9/15

N2 - 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 °C gives 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.

AB - 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 °C gives 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.

KW - 1,3,5-Triaza-7-phosphaadamantane

KW - 1,4,7-Triaza-9-phosphatricyclo[5.3.2]tridecane

KW - Pentacarbonyl complexes

KW - Rhenium

KW - Technetium

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U2 - 10.1016/j.jorganchem.2019.05.029

DO - 10.1016/j.jorganchem.2019.05.029

M3 - Article

AN - SCOPUS:85067051947

VL - 896

SP - 83

EP - 89

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -