Synthesis and characterization of uranyl thiolate complexes. Crystal and molecular structures of [Me4N][UO2(NO3)2(C5H4NS)] and [C16H25N2S2Si2][UO2(NO3)2(C8H12NSSi)]

Synthesis and Structural Characterization of a Uranyl(VI) Complex Possessing Unsupported Unidentate Thiolate Ligands

“…Similarly, the ν U  O stretch of 912 cm -1 is relatively unchanged with respect to the precursor dichloride complex (924 cm -1 ) . The U(1)−S(1) and U(1)−S(2) bond distances of 2.7143(7) and 2.7325(8) Å, respectively, are shorter than the corresponding U−S bond distances of 2.805(6) and 2.813(8) Å reported for [UO 2 ( o -C 5 H 4 NS)(NO 3 ) 2 ] - and [UO 2 ( o -C 5 H 4 NS-3-SiMe 3 )(NO 3 ) 2 ] - , respectively, which as mentioned above possess chelating pyridine-2-thiolate ligands. The U−S bond distances in 2b are comparable to those found in U(IV) complexes containing terminal thiolate ligands. , …”

“…Similarly, thiolate ligands are an important facet in coordination chemistry for a number of metals in a variety of oxidation states, but in striking contrast to the maturation of uranyl(VI) alkoxide chemistry, − the only structurally characterized thiolate complexes are represented by a few derivatives containing chelating pyridine-2-thiolate ligands. In these complexes, the ligands are anchored by the harder pyridine donors and possess a measure of resonance stabilization (Chart ) analogous to that of related dithiocarbamate ligands, as suggested by the relatively short U−N and long U−S bond distances observed in the solid-state structures. ,

1

…”

Final Report, Research Program to Investigate the Fundamental Chemistry of Technetium

“…In order to pursue these investigations, however, it was first necessary to devise improved methods for preparation of common starting materials. A number of technetium and rhenium complexes possessing terminal oxo or nitrido groups and halide ligands have been reported in the literature, but their widespread use has been hindered by difficult and low-yield syntheses (Cotton 1979, Davison 1982, Nelson 1954, Rulfs 1955, Liese 1981, Baldas 1991, Cotton 1966, Rose 1996, Baldas 1984 -, and MOX 3 (L) 2 (M = Tc, Re; X = Cl, Br, I; L = THF, MeCN) were devised. Vibrational and electronic spectroscopies proved best suited to characterize the metal oxohalide complexes; EPR spectroscopy was also utilized to examine the paramagnetic species in the series.…”

Thiosemicarbazone Complexes of Uranium(IV)

“…However, the ligand environment is much more rigid due to the connection to a benzothiazole ring in I-III and a mercaptopyridine in IV and V. The bond distances and angles are of similar values for I-V as in our complexes (UÀ S: 2.71-2.87 Å, UÀ N: 2.45-2.58 Å, SÀ UÀ N: 57-61°). There are also uranyl (VI) complexes with this four-membered coordination motif, [28][29][30] however, due to their different oxidation state these are not directly comparable.…”

“…The bond distances and angles are of similar values for I – V as in our complexes (U−S: 2.71–2.87 Å, U−N: 2.45–2.58 Å, S−U−N: 57–61°). There are also uranyl(VI) complexes with this four‐membered coordination motif, [28–30] however, due to their different oxidation state these are not directly comparable.…”