Rhodium Phosphine Olefin Complexes of the Weakly Coordinating Anions [BArF4]- and [1-closo-CB11H6Br6]-. Kinetic vers

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• 作者：Thomas M. Douglas ; Eduardo Molinos ; Simon K. Brayshaw ; Andrew S. Weller
• 刊名：Organometallics
• 出版年：2007
• 出版时间：January 29, 2007
• 年：2007
• 卷：26
• 期：3
• 页码：463 - 465
• 全文大小：133K
• 年卷期：v.26,no.3(January 29, 2007)
• ISSN：1520-6041

文摘

Solution and solid-state structures for the pair ofcomplexes Rh{P(Cyp₂)(mages/gifchars/eta.gif" BORDER=0 >²-C₅H₇)}{mages/gifchars/eta.gif" BORDER=0 >⁶-(C₆H₃(CF₃)₂)BAr^F₃} andRh{P(Cyp₂)(mages/gifchars/eta.gif" BORDER=0 >²-C₅H₇)}(1-closo-CB₁₁H₆Br₆), which contain boundweakly coordinating anions, are reported. While thermochemicaldata show that enthalpically [1-closo-CB₁₁H₆Br₆]^- binds lessstrongly with the metal fragment and it is the large entropyloss for the overall process of coordination of the [BAr^F₄]^-anion that results in the latter anion being thermodynamicallymore weakly coordinating. Qualitative kinetic data arising fromreaction with H₂ indicates that the carborane anion is displacedmore readily, attributable to the ability of the carborane to lifta Rh-Br interaction.