TY - JOUR

T1 - Existence and Properties of [TcH(CO)5]

AU - Сахоненкова, Анна Павловна

AU - Мирославов, Александр Евгеньевич

AU - Сидоренко, Георгий

AU - Alberto, Roger

AU - Luca Besmer, Manuel

AU - Гуржий, Владислав Владимирович

AU - Тюпина, Маргарита Юрьевна

PY - 2024/6/10

Y1 - 2024/6/10

N2 - A preparation of [99TcH(CO)5] as a neat liquid oras a solution in a hydrocarbon solvent by treatment of[99TcBr(CO)5] with Na[BH4] in an organic solvent−water mixtureis presented. [99TcH(CO)5] was characterized by 1H and 99TcNMR spectroscopy, IR spectroscopy, and EI MS. The reactivity of[99TcH(CO)5] was studied. It reacts readily with strong acids suchas HClO4 and F3CCOOH to form [99Tc(ClO4)(CO)5] and[99Tc(O2C−CF3)(CO)5], respectively, but does not react withweak acids such as HCOOH. [99TcH(CO)5] is moderatelyresistant to atmospheric oxygen in solution and is more airsensitivein the neat form, gradually transforming into[99Tc3H(CO)14]. The metal−hydrogen bond in [99TcH(CO)5] isoxidized with I2 to form [99TcI(CO)5]. The oxidation pathwaywith molecular iodine differs from the ones observed for typical hydrides or acids and is rather characteristic for low-polarity covalentcompounds. The carbonyl groups of [99TcH(CO)5] are quite resistant to substitutions by σ-donor ligands. To promote suchsubstitutions, the Tc−H bond should be oxidatively cleaved. Unusual technetium carbonyl complexes, [(μ3-CO3)(99Tc(bipy)-(CO)3)3]99TcO4 and [99Tc(phen)2(CO)2]99TcO4, are formed in the reactions of [99TcH(CO)5] with 2,2′-bipyridine and 1,10-phenanthroline in air. [99Tc(phen)2(CO)2]+ is the first example of a technetium(I) dicarbonyl complex stabilized by ligands withweak π-acceptor properties.

AB - A preparation of [99TcH(CO)5] as a neat liquid oras a solution in a hydrocarbon solvent by treatment of[99TcBr(CO)5] with Na[BH4] in an organic solvent−water mixtureis presented. [99TcH(CO)5] was characterized by 1H and 99TcNMR spectroscopy, IR spectroscopy, and EI MS. The reactivity of[99TcH(CO)5] was studied. It reacts readily with strong acids suchas HClO4 and F3CCOOH to form [99Tc(ClO4)(CO)5] and[99Tc(O2C−CF3)(CO)5], respectively, but does not react withweak acids such as HCOOH. [99TcH(CO)5] is moderatelyresistant to atmospheric oxygen in solution and is more airsensitivein the neat form, gradually transforming into[99Tc3H(CO)14]. The metal−hydrogen bond in [99TcH(CO)5] isoxidized with I2 to form [99TcI(CO)5]. The oxidation pathwaywith molecular iodine differs from the ones observed for typical hydrides or acids and is rather characteristic for low-polarity covalentcompounds. The carbonyl groups of [99TcH(CO)5] are quite resistant to substitutions by σ-donor ligands. To promote suchsubstitutions, the Tc−H bond should be oxidatively cleaved. Unusual technetium carbonyl complexes, [(μ3-CO3)(99Tc(bipy)-(CO)3)3]99TcO4 and [99Tc(phen)2(CO)2]99TcO4, are formed in the reactions of [99TcH(CO)5] with 2,2′-bipyridine and 1,10-phenanthroline in air. [99Tc(phen)2(CO)2]+ is the first example of a technetium(I) dicarbonyl complex stabilized by ligands withweak π-acceptor properties.

UR - https://www.mendeley.com/catalogue/02d1bf84-f066-31f8-8032-427de3145233/

U2 - 10.1021/acs.organomet.4c00083

DO - 10.1021/acs.organomet.4c00083

M3 - Article

VL - 43

SP - 1233

EP - 1245

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 11

ER -