Self-assembly of {W₂O₄}^2 +: Syntheses and structures of high-valent tungsten compounds

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• 作者：Barbara Modec ; ^{barbara.modec@fkkt.uni-lj.si" class="auth_mail} ; Jurij V. Bren膷i膷¹
• 关键词：Tungsten(V) coordination compounds ; Clusters ; Mixed-valence species ; {WV2O4}2  ; + structural unit ; Crystal structure
• 刊名：Inorganic Chemistry Communications
• 出版年：April, 2014
• 年：2014
• 卷：42
• 期：Complete
• 页码：5-9
• 全文大小：682 K

文摘

Oxidation of K₃[W^III₂Cl₉] in the mixture of concentrated hydrochloric acid and pyridine in the presence of hydrazinium dichloride afforded (PyH)₅[W^VOCl₄(H₂O)]₃Cl₂ (PyH⁺ = pyridinium cation, C₅H₅NH⁺) (1), obtained as emerald green needle-shaped crystals. The compound contains mononuclear octahedrally shaped [WOCl₄(H₂O)]^{鈭?/sup> ions. In contrast to its molybdenum analog, 1 shows a marked instability in the air. Solvothermal reaction of a tetrabutylammonium salt of the [WOCl₄(H₂O)]鈭?/sup> ion with pyridine at 115 掳C afforded a small amount of orange crystals of [WV₈WVI₂O₂₆(Py)₈]路Py (2) (Py = pyridine, C₅H₅N). The WV centers can be clearly distinguished from the WVI sites, namely they are grouped into four metal-metal bonded {WV₂O₄}2 + cores. The structure of the cluster is virtually identical with the analogous molybdenum complex, [Mo₁₀O₂₆(Py)₈]. The isolation of [W₁₀O₂₆(Py)₈]路Py (2) confirms that the {W₂O₄}2 + core forms from the [WOCl₄(H₂O)]鈭?/sup> ions upon the substitution of the labile ligands.}