Synthesis and spectroscopic characterization of eleven mixed-ligand diorganotellurium(IV) compounds containing dithiocarbamate and dithiophosphate ligands

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• 作者：Ave Mar&#xed ; a Cotero-Villegas^a ; ; Patricia Garc&#xed ; a y Garc&#xed ; a^b ; Herbert Hö ; pfl^b ; Mar&#xed ; a del Carmen Pé ; rez-Redondo^a ; Patricia Mart&#xed ; nez-Salas^b ; Marcela Ló ; pez-Cardoso^b ; Raymundo Cea Olivares^c ; ^{cea@servidor.unam.mx}
• 关键词：Dithiocarbamate ; Dithiophosphate ; Organotellurium (IV) ; Tellurocycles ; Mixed-ligand compounds ; Single-crystal X-ray diffraction analysis
• 刊名：Journal of Organometallic Chemistry
• 出版年：2011
• 出版时间：15 May 2011
• 年：2011
• 卷：696
• 期：10
• 页码：2071-2078
• 全文大小：704 K

文摘

Eleven mixed-ligand organotellurium(IV) compounds of composition R₂Te(dtc)(dtp) have been prepared employing two different dithiocarbamate (dtc) and dithiophosphate (dtp) ligands: 1, R₂ = C₄H₈, dtc = S₂CNEt₂, dtp = S₂P(OCH₂)₂CEt₂; 2, R₂ = C₈H₈, dtc = S₂CNEt₂, dtp = S₂P(OCH₂)₂CEt₂; 3, R₂ = C₄H₈O, dtc = S₂CNEt₂, dtp = S₂P(OCH₂)₂CEt₂; 4, R₂ = C₅H₁₀, dtc = S₂CNEt₂, dtp = S₂P(OCH₂)₂CEt₂; 5, R₂ = C₄H₈, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CEt₂; 6, R₂ = C₈H₈, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CEt₂; 7, R₂ = C₄H₈O, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CEt₂; 8, R₂ = C₅H₁₀, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CEt₂; 9, R₂ = C₄H₈, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CMeⁿPr; 10, R₂ = C₈H₈, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CMeⁿPr; 11, R₂ = C₄H₈O, dtc = S₂CN(CH₂)₄, dtp = S₂P(OCH₂)₂CMeⁿPr. 1–11 were characterized by mass spectrometry, IR spectroscopy and multinuclear NMR (¹H, ¹³C, ³¹P, ¹²⁵Te) spectroscopy. The molecular structures of 2, 4 and 6, of which 2 crystallized in form of two different polymorphs (2a and 2b), were analyzed by single-crystal X-ray diffraction analysis. This analysis showed that the coordination mode of both ligand types is anisobidentate. When considering only covalent Te–C and Te–S bonds, the coordination geometry of the tellurium atoms is distorted Ψ-trigonal-bipyramidal, since the lone pair is stereochemically active and occupies an equatorial position together with the carbon atoms of the tellurocycles. If secondary TeS interactions are considered also, the coordination sphere around tellurium is best described as bicapped Ψ-trigonal-bipyramidal for the complexes with two intramolecular TeS secondary bonds and monomeric molecular structures, and pentagonal-bipyramidal for the complexes in which neighboring molecules in the crystal lattice are linked through additional weak intermolecular TeS secondary bonds to form dimeric supramolecular aggregates.