Metal clusters in catalysis. II. Electron spin resonance study of dinuclear metal complex fragments and their interaction with organic substrates
Metal clusters in catalysis. II. Electron spin resonance study of dinuclear metal complex fragments and their interaction with organic substrates
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催化中的金属簇。
DOI：
10.1021/ja00851a057
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发表时间：
1975
影响因子：
15
通讯作者：
K. Zamaraev
中科院分区：
文献类型：
--
作者：
E. Muetterties;B. Sosinsky;K. Zamaraev
（ch3） 3] 7。此外，簇中最弱的键通常被证明是框架簇键；因此，有进一步的可能产生可逆反应片段的簇络合物。在这种情况下，最简单、最容易获得的一类化合物包括双核金属配合物。在这里，我们描述了一组易解离的铁配合物，[（烯丙基）Fe (CO) 2L] 2，催化化学和ESR研究，该研究提供了：(1)Fe-Fe键能的精确测量，(2)（烯丙基）Fe (CO) 3与不饱和有机底物相互作用的动力学，热力学和电子观点，以及(3)证明在每个系统中通常存在两个单核异构体，并且这些异构体具有高通量。双核[CsHsFetCO^ h]配合物A在溶液中解离得到顺磁性物质。均衡原本被认为是复杂的，现在却被证明是单一的。在+ 40 ~ 90温度范围内对ESR信号积分强度的分析表明，a的溶液状态完全由解离反应表征。
(CH3) 3] 7. In addition, the weakest bonds in clusters may often proveto be the framework cluster bonds; 2 hence there is the further potentialin cluster complexes of reversibly generating reactive fragments. In this context, the simplest, most readily available class comprises dinuclear metal com-plexes. Herein we describe for a group of readilydissociable iron complexes,[(allyl) Fe (CO) 2L] 2, catalytic chemistry and an ESR study that provides,(1) an accurate measure of Fe-Fe bond energies,(2) a kinetic, thermodynamic, and electronic view of the interaction of (allyl) Fe (CO) 3 with unsaturated organic substrates, and (3) a demonstration that two mononuclear isomers are usually present in each system and that these are highly fluxional. The binuclear [CsHsFetCO^ h complex, A, dissociates in solution to give a paramagnetic species. Equilibria, presumed to be complex, 33 are now shown to be singular. Anal-ysis of ESR signal integral intensities over a temperature range of+ 40 to—90 establish that the solution state of A is fully4 represented by dissociation 1.