Research output: Contribution to journal › Article › peer-review
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: Contribution to journal › Article › peer-review
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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
UR - http://www.scopus.com/inward/record.url?scp=85067051947&partnerID=8YFLogxK
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 -
ID: 45083844