Anna P. Sakhonenkova, Alexander E. Miroslavov*, Georgy V. Sidorenko, Roger Alberto, Manuel Luca Besmer, Vladislav V. Gurzhiy and Margarita Yu. Tyupina,
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引用次数: 0
Abstract
A preparation of [99TcH(CO)5] as a neat liquid or as a solution in a hydrocarbon solvent by treatment of [99TcBr(CO)5] with Na[BH4] in an organic solvent–water mixture is presented. [99TcH(CO)5] was characterized by 1H and 99Tc NMR spectroscopy, IR spectroscopy, and EI MS. The reactivity of [99TcH(CO)5] was studied. It reacts readily with strong acids such as HClO4 and F3CCOOH to form [99Tc(ClO4)(CO)5] and [99Tc(O2C–CF3)(CO)5], respectively, but does not react with weak acids such as HCOOH. [99TcH(CO)5] is moderately resistant to atmospheric oxygen in solution and is more air-sensitive in the neat form, gradually transforming into [99Tc3H(CO)14]. The metal–hydrogen bond in [99TcH(CO)5] is oxidized with I2 to form [99TcI(CO)5]. The oxidation pathway with molecular iodine differs from the ones observed for typical hydrides or acids and is rather characteristic for low-polarity covalent compounds. The carbonyl groups of [99TcH(CO)5] are quite resistant to substitutions by σ-donor ligands. To promote such substitutions, 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 with weak π-acceptor properties.
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.