Reaction of technetium hexacarbonyl cation with acetonitrile: Kinetics, product structure, DFT calculations

Synthesis of [99Tc(CO)6]+ Cation under Ambient Conditions

“…As seen from the spectrum (Figure S4), no bands other than the bands of Nujol, [ 99 Tc(CO) 6 ] + and ClO 4 − are present. The IR spectrum of a solution of the product in acetonitrile in the range of the stretching vibrations of carbonyl groups contains only the band at 2094.6 cm −1 assigned to [ 99 Tc(CO) 6 ] + (Figure S5) [8] . The elemental analysis of the product for Tc matched well the formula [ 99 Tc(CO) 6 ]ClO 4 (see the Experimental Section).…”

“…To decrease the reaction temperature and pressure, we used [ 99 Tc(ClO 4 )(CO) 5 ] as the starting compound. By treatment of dichloromethane solution of this compound with carbon monoxide at room temperature at a pressure of 110 atm overnight, we obtained [ 99 Tc(CO) 6 ]ClO 4 in a yield of 30 % [8] . Thus, all procedures currently known for preparing technetium hexacarbonyl require a high pressure of carbon monoxide.…”

“…By treatment of dichloromethane solution of this compound with carbon monoxide at room temperature at a pressure of 110 atm overnight, we obtained [ 99 Tc(CO) 6 ]ClO 4 in a yield of 30 %. [8] Thus, all procedures currently known for preparing technetium hexacarbonyl require a high pressure of carbon monoxide. The aim of this study was preparation of this compound under ambient conditions.…”

“…[2] Until recently, there were no reports on synthesis of higher technetium carbonyls (CO : Tc > 3) at atmospheric pressure (the compound [ 99 Tc 3 H 3 (CO) 12 ] reported by Alberto et al [3] seems to be the only exception). All the syntheses were performed at high CO pressures, [4][5][6][7][8] which does not comply with the modern safety requirements adopted in the majority of developed countries. Recently we reported the atmospheric-pressure synthesis of [ 99 TcHal(CO) 5 ], [9] which makes a wide range of higher technetium carbonyls synthetically accessible without using high CO pressures (subsequent transformations of [ 99 TcHal(CO) 5 ] into diverse tetra-and pentacarbonyl complexes are performed at ambient pressure [10][11][12][13] ).…”

Синтез И Устойчивость В Биологической Среде [99tc(co)6 ]+

“…Нашей научной группой был предложен метод синтеза катиона гексакарбонила технеция (I), [ 99 Tc(CO) 6 ] + [2], который является химическим аналогом широко применяющегося кардиотропа 99m Tc-MIBI. В настоящей работе предлагается новая методика, позволяющая получить [ 99 Tc(CO) 6 ] + при атмосферном давлении CO в присутствии AlCl 3 в качестве катализатора.…”