Hydrolysis of Hexacarbonyltechnetium(I) Cation: Formation and Structure of Technetium Carbonyl Hydride 99Tc3H(CO)14

Alexander E Miroslavov; Anna P Shishkina; Georgy V Sidorenko; Vladislav V Gurzhiy; Daniil A Maltsev; Ekaterina V Kurysheva

doi:10.1021/acs.inorgchem.0c01145

Hydrolysis of Hexacarbonyltechnetium(I) Cation: Formation and Structure of Technetium Carbonyl Hydride ⁹⁹Tc₃H(CO)₁₄

Inorg Chem. 2020 Jul 6;59(13):9239-9243. doi: 10.1021/acs.inorgchem.0c01145. Epub 2020 Jun 16.

Authors

Alexander E Miroslavov^{1

2}, Anna P Shishkina^{1

2}, Georgy V Sidorenko¹, Vladislav V Gurzhiy³, Daniil A Maltsev⁴, Ekaterina V Kurysheva¹

Affiliations

¹ Khlopin Radium Institute, 2nd Murinskii pr. 28, St. Petersburg, 194021 Russia.
² Radiochemical Department, St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg, 199034 Russia.
³ Department of Crystallography, Institute of Earth Sciences, St. Petersburg State University, Universitetskaya nab. 7/9, St. Petersburg, 199034 Russia.
⁴ Petersburg Nuclear Physics Institute, mkr. Orlova roshcha 1, Gatchina, Leningrad oblast 188300 Russia.

PMID: 32543190
DOI: 10.1021/acs.inorgchem.0c01145

Abstract

Reaction of [⁹⁹Tc(CO)₆]ClO₄ with alkali in aqueous solutions yields yellow ⁹⁹Tc₃H(CO)₁₄ as the major product. On the other hand, [⁹⁹TcH(CO)₅] becomes the major product when the reaction with alkali is combined with the extraction into hexane. The molecular structure of ⁹⁹Tc₃H(CO)₁₄, determined by SCXRD, is composed of the ⁹⁹Tc₂(CO)₉ fragment bound to the ⁹⁹Tc(CO)₅ fragment via the hydrogen bridge and weak metal-metal bond. This compound crystallizes in the monoclinic system, space group P2₁/n, a = 9.6954(2) Å, b = 15.0985(3) Å, c = 14.5090(3) Å, and β = 104.925(2)°. ⁹⁹Tc₃H(CO)₁₄ was additionally characterized by IR spectroscopy. The mechanism of hydrolysis of [⁹⁹Tc(CO)₆]ClO₄ was suggested.