New Fe(III) and Os(VI) silsesquioxanes

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• 作者：Shapley ; Patricia A. ; Bigham ; W. Stuart ; Hay ; Michael T.
• 关键词：Silsesquioxane ; Metallasilsesquioxane ; Fe(III) ; Cysteine ; Nitridoosmium
• 刊名：Inorganica Chimica Acta
• 出版年：2002
• 出版时间：March 10, 2002
• 年：2002
• 卷：345
• 期：Complete
• 页码：255-260
• 全文大小：163 K

文摘

The high-spin iron(III) silsesquioxane complexes [N(ⁿBu)₄][(cyclo-C₅H₉)₇Si₇O₁₂FeCl] and [N(ⁿBu)₄][(cyclo-C₅H₉)₇Si₇O₁₂Fe(OSiMe₃)] result from the reaction of (cyclo-C₅H₉)₇Si₇O₉(OH)₃ with either [N(ⁿBu)₄][FeCl₄] or [N(ⁿBu)₄][Fe(OSiMe₃)₄]. Substitution of the terminal chloride or (trimethyl)silanolate ligands with tert-butoxide produces [N(ⁿBu)₄][(cyclo-C₅H₉)₇Si₇O₁₂Fe(OCMe₃)]. Similar substitution reactions with the methyl ester of N-acetylcysteine produce [N(ⁿBu)₄][(cyclo-C₅H₉)₇Si₇O₁₂Fe{SCH₂CH(NHCOCH₃)CO₂Me}]. A dimeric complex, [(cyclo-C₅H₉)₇Si₇O₁₂Fe(NEt₃)]₂, forms in the reaction of (cyclo-C₅H₉)₇Si₇O₉(OH)₃ with NEt₃ and FeCl₃. The reaction between (cyclo-C₅H₉)₇Si₇O₉(OH)₂(OSiMe₃) and [Ph₄P][Os(N)Cl₄] forms [PPh₄][(cyclo-C₅H₉)₇Si₇O₁₁(OSiMe₃)Os(N)Cl₂], a square-pyramidal Os(VI) complex with a bidentate siloxy ligand.