First evidence for the formation of technetium oxosulfide complexes: synthesis, structure and characterization.

The reaction of tetrabutylammonium pertechnetate with bis(trimethylsilyl) sulfide in solution was studied by UV-Visible spectroscopy and mass spectrometry. Experimental results and density functional calculations provide the first evidence for the formation of a TcO(3)S(-) precursor. Larger scale synthesis afforded a solid that was characterized by EDX and XANES spectroscopy. XANES showed the presence of technetium in tetravalent state. EDX indicated the solid contained technetium, sulfur and oxygen.

[1]  Edward J. Mausolf,et al.  Spectroscopic and structural characterization of reduced technetium species in acetate media , 2011 .

[2]  W. Lukens,et al.  Speciation of heptavalent technetium in sulfuric acid: structural and spectroscopic studies. , 2010, Dalton transactions.

[3]  Eunja Kim,et al.  First-principles study of the hexahalogenotechnetate(IV) ions TcX62- [X = Cl, Br] , 2010 .

[4]  F. Poineau,et al.  Octachloro- and octabromoditechnetate(III) and their rhenium(III) congeners. , 2008, Inorganic chemistry.

[5]  S. Jurisson,et al.  Pertechnetate immobilization in aqueous media with hydrogen sulfide under anaerobic and aerobic environments , 2007 .

[6]  W. Lukens,et al.  Evolution of technetium speciation in reducing grout. , 2005, Environmental science & technology.

[7]  R. H. Holm,et al.  Oxygen/sulfur substitution reactions of tetraoxometalates effected by electrophilic carbon and silicon reagents. , 2004, Inorganic chemistry.

[8]  R. Cotton,et al.  Permanganate Oxidation Reactions of DNA: Perspective in Biological Studies , 2003, Nucleosides, nucleotides & nucleic acids.

[9]  S. H. Laurie.  Thiomolybdates — Simple but Very Versatile Reagents , 2000 .

[10]  E. Baerends,et al.  The d0, d1 and d2 Configuration in Known and Unknown Tetrathiometal Compounds MS4n- (M=Mo,Tc,Ru; W,Re,Os), A Quantum Chemical Study. , 1999 .

[11]  V. Barone,et al.  Toward reliable density functional methods without adjustable parameters: The PBE0 model , 1999 .

[12]  T. Ressler.  WinXAS: a program for X-ray absorption spectroscopy data analysis under MS-Windows. , 1998, Journal of synchrotron radiation.

[13]  A. Degl'innocenti,et al.  Organosilanes in Sulfur Chemistry: Silicon Mediated Synthesis and Reactivity of Sulfur-Containing Molecules , 1998 .

[14]  W. Herrmann,et al.  Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications. , 1997, Chemical reviews.

[15]  Anthony K. Burrell,et al.  ELECTRONIC AND STRUCTURAL INVESTIGATIONS OF TECHNETIUM COMPOUNDS BY X-RAY-ABSORPTION SPECTROSCOPY , 1995 .

[16]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[17]  J. Rehr,et al.  Near-edge x-ray-absorption fine structure of Pb: A comparison of theory and experiment. , 1993, Physical review. B, Condensed matter.

[18]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[19]  K. Dwight,et al.  Low Temperature Synthesis of Transition Metal Sulfides , 1992 .

[20]  H. Stoll,et al.  Energy-adjustedab initio pseudopotentials for the second and third row transition elements , 1990 .

[21]  D. Schleich,et al.  New low-temperature synthesis of transition-metal sulfides , 1988 .

[22]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[23]  A. Müller,et al.  Transition Metal Thiometalates: Properties and Significance in Complex and Bioinorganic Chemistry , 1981 .

[24]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[25]  F. L. Hirshfeld.  Bonded-atom fragments for describing molecular charge densities , 1977 .

[26]  A. Müller,et al.  The assignments of electron transfer bands of molybdates (VI), tungstates (VI) and rhenates (VII) of the type MXY3(C3V) (X,YO,S,Se) , 1972 .

[27]  A. Müller,et al.  Übergangsmetallchalkogenverbindungen. Evidence for the Existence of MoO3S2− and WO3S2− Ions in aqueous solution , 1969 .

[28]  R. Hirsch,et al.  TECHNETIUM CHEMISTRY, OXIDATION STATES AND SPECIES , 1967 .

[29]  A. Allred,et al.  Electronegativity values from thermochemical data , 1961 .

[30]  G. Ouvrard,et al.  XAS study of technetium(IV) polymer formation in mixed sulphate/chloride media , 2002 .

[31]  C. A. Langton,et al.  Technetium Speciation in Cement Waste Forms Determined by X-ray Absorption Fine Structure Spectroscopy , 1997 .

[32]  W. Newton,et al.  Syntheses and characterization of ammonium and tetraalkylammonium thiomolybdates and thiotungstates , 1983 .