National Institute of Advanced Industrial Science and Technology, Tsukuba Central 5-2, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan.
Dalton Trans. 2013 Jul 14;42(26):9628-36. doi: 10.1039/c3dt50445j. Epub 2013 May 15.
A series of highly functionalized cyclopentadienyl rhodium(III) complexes, Cp'Rh(bpy)Br (Cp' = substituted cyclopentadienyl), was synthesized from various multi-substituted cyclopentadienes (Cp'H). [Rh(cod)Cl]2 and Cp'H were firstly converted to [Cp'Rh(cod)] complexes, which were then treated with Br2 to give the rhodium(III) dibromides [Cp'RhBr2]2. The novel complexes Cp'Rh(bpy)Br were obtained readily by the reaction of 2,2'-bipyridine with [Cp'RhBr2]2. These rhodium complexes Cp'Rh(bpy)Br were fully characterized and utilized in the hydrogenation of cyclohexanone and acetophenone with generally high yields, but they did not exhibit the same reactivity trends for the two substrate ketones. The different activity of these complexes for the different substrates may be due to the influence of the substituents on the Cp' rings.
一系列高度功能化的环戊二烯基铑(III)配合物，Cp'Rh(bpy)Br（Cp'=取代的环戊二烯基），是由各种多取代的环戊二烯（Cp'H）合成的。[Rh(cod)Cl]2和 Cp'H 首先转化为[Cp'Rh(cod)]配合物，然后用 Br2 处理得到铑(III)二溴化物[Cp'RhBr2]2。新型配合物Cp'Rh(bpy)Br通过 2,2'-联吡啶与[Cp'RhBr2]2 的反应很容易得到。这些铑配合物Cp'Rh(bpy)Br经过充分表征，并用于环己酮和苯乙酮的加氢反应，通常具有很高的收率，但它们对两种底物酮的反应性趋势并不相同。这些配合物对不同底物的不同活性可能归因于 Cp'环上取代基的影响。
