Iridium-Ruthenium-gold cluster complexes: Structures, and skeletal Rearrangements

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• 作者：Richard D. Adams ; ^{Adams@mail.chem.sc.edu} ; Perry J. Pellechia ; Mark D. Smith ; Qiang Zhang
• 关键词：Cluster ; Trimetallic ; Gold ; Iridium ; Ruthenium
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：1 June, 2012
• 卷：706-707
• 期：Complete
• 页码：20-25
• 文件大小：696 K

摘要

Three new IrRuAu trimetallic cluster complexes: IrRu₃(CO)₁₃AuPPh₃, rong class="boldFont">1rong>, HIrRu₃(CO)₁₂(AuPPh₃)₂, rong class="boldFont">2rong> and IrRu₃(CO)₁₂(AuPPh₃)₃, rong class="boldFont">3rong> were obtained in low yields from the reaction of HIrRu₃(CO)₁₃ with [(AuPPh₃)₃O][BF₄]. Compounds rong class="boldFont">1rong> and rong class="boldFont">3rong> were subsequently obtained in much better yields (82%) and (84%) from the reactions of [AuPPh₃][NO₃] and [(AuPPh₃)₃O][BF₄] with [PPN][IrRu₃(CO)₁₃], respectively. The molecular structures of all three compounds were established by single crystal x-ray diffraction methods. Compounds rong class="boldFont">1rong> and rong class="boldFont">2rong> contain an Au(PPh₃) group that bridges one triangular face of a tetrahedral IrRu₃ cluster. Compound rong class="boldFont">2rong> contains a second Au(PPh₃) capping group that bridges an Ir-Ru-Au triangle. Compound rong class="boldFont">3rong> consists of a pentagonal bipyramidal Au₃IrRu₃ cluster that has three gold atoms and two of the ruthenium atoms in the equatorial plane. There is a bond between the apical Ir and Ru atoms. Compounds rong class="boldFont">2rong> and rong class="boldFont">3rong> exhibit dynamical activity in the metal skeleton that leads to a rapid averaging of the inequivalent Au(PPh₃) groups on the NMR timescale at room temperature.