New series of intramolecularly coordinated diaryltellurium compounds. Rational synthesis of the diarylhydroxytelluronium triflate [(8-Me 2NC 10H 6) 2Te(OH)](O 3SCF 3)
Data(s) |
01/01/2012
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Resumo |
The reaction of 8-dimethylaminonaphthyllithium etherate with the tellurium(II) bis(dithiocarbamate) Te(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2 </sub>provided the diaryltelluride (8-Me<sub>2</sub>NC<sub>10</sub>H<sub>6</sub>)<sub>2</sub>Te (1). The oxidation of 1 with an excess of H<sub>2</sub>O<sub>2</sub> did not afford the expected diaryltellurium(IV) oxide (8-Me<sub>2</sub>NC<sub>10</sub>H<sub>6</sub>)<sub>2</sub>TeO (2), but the diaryltellurium(VI) dioxide (8-Me<sub>2</sub>NC<sub>10</sub>H<sub>6</sub>)<sub>2</sub>TeO<sub>2</sub> (3). The preparation of 2 was achieved by the comproportionation reaction of 1 and 3. The protonation of 2 using triflic acid gave rise to the formation of diarylhydroxytelluronium triflate [(8-Me<sub>2</sub>NC<sub>10</sub>H<sub>6</sub>)<sub>2</sub>Te(OH)](O<sub>3</sub>SCF<sub>3</sub>) (4), which features the protonated diaryltellurium oxide [(8-Me<sub>2</sub>NC<sub>10</sub>H<sub>6</sub>)<sub>2</sub>Te(OH)]+ (4a). Compounds 1, 3·H<sub>2</sub>O·H<sub>2</sub>O<sub>2</sub>, 3·2H<sub>2</sub>O, and 4 were characterized by X-ray crystallography. The experimentally obtained molecular structures were compared to those calculated for 1–3, 4a, and (8-Me<sub>2</sub>NC<sub>10</sub>H<sub>6</sub>)<sub>2</sub>Te(OH)<sub>2</sub> (5) as well as the related diphenyltellurium compounds Ph<sub>2</sub>Te (6), Ph<sub>2</sub>TeO (7), Ph<sub>2</sub>TeO<sub>2</sub> (8), [Ph<sub>2</sub>Te(OH)]+ (9a), and Ph<sub>2</sub>Te(OH)<sub>2</sub> (10) at the DFT/B3PW91 level of theory.<br /> |
Identificador | |
Idioma(s) |
eng |
Publicador |
American Chemical Society |
Relação |
http://dro.deakin.edu.au/eserv/DU:30047047/duthie-newseriesof-2012.pdf http://dx.doi.org/10.1021/om2008259 |
Direitos |
2011, American Chemical Society |
Palavras-Chave | #photosensitized oxygenation #diorganotellurium oxides #oxidizing properties #diaryl tellurides #thiol peroxidase #transfer reagent #metal-carbonyls #co substitution #atom transfer #x-ray |
Tipo |
Journal Article |