16834-15-4Relevant academic research and scientific papers
Structures of dimethyl earthmetal phenylchalcogenolates [(Me 2MEPh)n] withM = Ga, In, Tl and e = S, Se, Te
Kluge, Oliver,Gerber, Stefan,Krautscheid, Harald
, p. 1909 - 1921 (2012/01/12)
The reaction of main group III trimethyls, Me3M, with phenylchalcogenols HEPh leads to dimethyl earthmetal phenylchalcogenolates [(Me2MEPh)n] with M = Ga and E = S (1), Se (2), Te (3), M = In and E = S (4), Se (5), Te (6) and M = Tl and E = S (7), Se (8), Te (9). Alternatively, reaction between Me3M and Me3SiEPh with elimination of SiMe4 is possible for E = Se, Te if a polar solvent is applied, in order to stabilize the initial adduct [Me3M-E(Ph) SiMe3]. Additionally, for M = Tl and E = S the dimeric adduct [{Me2TlSPh(TlMe3)}2] (10) was isolated and structurally characterized. Single crystals and microcrystalline samples of compounds 1 to 9 were examined by X-ray crystallography and polymeric as well as dimeric structures were found. Depending on the size of main group III and VI atoms, sterically shielded polymeric chains or layer-like structures are obtained. The smaller metal atoms M = Ga, In are fourfold coordinated and these compounds exhibit polymorphism. This observation is consistent with quantum chemical calculations that show the syn- and anti-orientation of phenyl groups in a dimer to be energetically nearly equivalent. For M = Tl the coordination number is increased to 5 or 6 by additional coordination of chalcogen atoms with relatively long Tl-E bonds. Variable temperature NMR spectroscopy and molecular weight measurements indicate fast exchange and the presence of several different molecular structures in solution. Copyright
Dimethylthallium(III) complexes with S,N and S,O ligands: The molecular structure of Me2TlL (L = 1-oxidopyridinium-2-thiolato)
Casta?o, María V.,Sánchez, Agustin,Casas, José S.,Sordo, José,Briansó, José L.,Piniella, Juan F.,Solans, Xabier,Germain, Gabriel,Debaerdemaeker, Tony,Glaser, Julius
, p. 1897 - 1904 (2008/10/08)
The reaction of heterocyclic thiolic derivatives HLn with dimethylthallium(III) hydroxide yields Me2TlL compounds. The structure of dimethyl(1-oxidopyridinium-2-thiolato)thallium(III), Me2TlL5, has been determined by X-ray analysis. Me2TlL5 crystals are monoclinic, space group P21/c, with a = 9.812 (3) ?, b = 7.616 (1) ?, c = 12.851 (3) ?, β = 97.48 (3) °, and Z = 4. The structure was refined to R = 0.016 for 929 unique data. In this compound the thallium atom is six-coordinate, if weak bridging interactions are considered, in lattices with polymeric chains. Spectroscopic data for the complexes (1H, 13C, and 205Tl NMR, IR, and Raman) are discussed in order to determine possible structural/spectroscopic correlations.
