Multi-electron reduction from alkyl/hydride ligand combinations in U4+ complexes
Multi-electron reduction from alkyl/hydride ligand combinations in U4+ complexes
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DOI：
10.1021/ja805107v
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发表时间：
2008-09-17
影响因子：
15
通讯作者：
Miller, Kevin A.
中科院分区：
文献类型：
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作者：
Evans, William J.;Montalvo, Elizabeth;Miller, Kevin A.
U ~（4+）混合烃基氢化物配合物（C_5Me_5）U[mu-C_5 Me_3（CH_2）（2）]（mu-H）（2）U（C_5M_5）（2），1，它含有一个带有两个金属化亚甲基取代基的双金属配体，和八电子还原，其中两个H1-配体和[C5 Me 3（CH 2）（2）]（3-）部分的组合传递四个电子并形成（C5 Me 5）（1-）。该反应在形式上等同于烷基氢化物还原消除，这是一种过渡金属常见的转化，以前在f元素化合物中没有观察到。这种类型的烷基氢化物还原反应性也在U4+烷基和氢化物络合物的组合（C5 Me 5）（2）UMe 2/[（C5 Me 5）（2）UH 2]（2）中观察到，其还原苯以产生[（C5 Me 5）（2）U]（2）（C6 H6），一种形式上含有（C6 H6）（2-）配体的U3+络合物。
The U4+ mixed alkyl hydride complex (C5Me5)U[mu-C5Me3(CH2)(2)] (mu-H)(2)U(C5M5)(2), 1, which contains a cyclopentadienyl ligand with two metalated methylene substituents, can effect four, six, and eight-electron reductions in which the combination of the two H1- ligands and the [C5Me3(CH2)(2)](3-) moiety delivers four electrons and forms (C5Me5)(1-). The reaction is formally equivalent to an alkyl hydride reductive elimination, a transformation common with transition metals not previously observed with f element compounds. This type of alkyl hydride reduction reactivity is also observed with a combination of U4+ alkyl and hydride complexes, (C5Me5)(2)UMe2/[(C5Me5)(2)UH2](2), which reduces benzene to make [(C5Me5)(2)U](2)(C6H6), a U3+ complex formally containing a (C6H6)(2-) ligand.