New diorganoselenium(II) compounds and their behavior toward late transition metals

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• 作者：Alex ; ra Pop ; Dragos Rosca ; Raluca Mitea ; Anca Silvestru
• 关键词：Hypervalent organoselenium(II) compounds ; Late transition metal complexes ; NMR spectroscopy ; Mass spectrometry ; Single-crystal X-ray diffraction
• 刊名：Inorganica Chimica Acta
• 出版年：2013
• 出版时间：24 August, 2013
• 年：2013
• 卷：405
• 期：Complete
• 页码：235-242
• 全文大小：953 K

文摘

Hypervalent diorganoselenium(II) compounds of type 1-{2-[(2-(3,5-dimethyl-4,5-dihydro-1H-pyrazol-1-yl)ethyl)selanyl]phenyl}-N,N-dialkylmethanamine, [2-(R₂NCH₂)C₆H₄][(3,5-dmpz)CH₂CH₂]Se, [R = Me (1), Et (2), dmpz = dimethylpyrazole] were obtained by reacting 1-(2-bromoethyl)-3,5-dimethyl-1H-pyrazole [(3,5-dmpz)CH₂CH₂Br] with alkali metal aryl selenolates of type [2-(R₂NCH₂)C₆H₄]SeM (R = Me, M = Na; R = Et, M = Li) in a 1:1 molar ratio. The coordination ability of species 1, as well as that of bis[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl]selane, [(3,5-dmpz)CH₂CH₂]₂Se (3) toward several late transition metals (Pd, Au, Ag) was investigated by reacting the neutral ligands 1 and 3 with PdCl₂, AuCl(tht) and AgOTf in a 1:1 molar ratio. The neutral ligands 1-3, as well as the gold(I), silver(I) and palladium(II) adducts [2-(Me₂NCH₂)C₆H₄][(3,5-dmpz)CH₂CH₂)]SeAuCl (4), [(3,5-dmpz)CH₂CH₂)]₂SeAuCl (5), [2-(Me₂NCH₂)C₆H₄][(3,5-dmpz)CH₂CH₂)]SeAgOTf (6), [(3,5-dmpz)CH₂CH₂)]₂SeAgOTf (7) and [(3,5-dmpz)CH₂CH₂)]₂SePdCl₂ (8) were characterized by NMR spectroscopy (¹H, ¹³C, ⁷⁷Se) and mass spectrometry. The reaction between 1 and PdCl₂ in a 1:1 molar ratio resulted in the formation of a complex reaction mixture of which the species [2-(Me₂NCH₂)C₆H₄SePdCl]₂ (9) and 1-(2-chloroethyl)-3,5-dimethyl-1H-pyrazole [(3,5-dmpz)CH₂CH₂Cl] were unambiguously identified. Single crystal X-ray diffraction studies revealed a monomeric structure with a distorted T-shaped coordination geometry of type (C,N)SeC for the neutral ligand 1 and supramolecular associations based on dimeric units in case of species 9 and 9¡¤0.5CH₂Cl₂¡¤0.5THF.