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

1 Citation (Scopus)

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

Scopus subject areas

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

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