Raghavan Adharsh, Yuan Fang, Ren Tong
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
Inorg Chem. 2020 Jul 6;59(13):8663-8666. doi: 10.1021/acs.inorgchem.0c01755. Epub 2020 Jun 22.
Reported herein is the use of aryls as axial ligands to manipulate reactivity at the distal metal site through metal-metal-ligand interactions in diruthenium paddlewheel complexes. The vacant ruthenium site in Ru(ap)(Ar) (; ap = 2-anilinopyridinate and Ar = CH-4-NMe), thus rendered reactive, is able to bind a series of isoelectronic ligands to afford three complexes of the form (Y)Ru(ap) [Y = CN (), HC≡C (), CO ()], each of which exhibits a distinct electronic structure. While reactions with anionic ligands subsequently result in oxidation of the diruthenium core from Ru(II,III) to Ru(III,III), the reaction with CO yields a rare example of a Ru(II,III)-CO adduct. The latter reaction is particularly interesting in its completely reversible change of the ground state from = / in to = / in , the first of its kind seen in Ru(II,III) species. In general, this work sheds light on the modulation of the electronic structure of diruthenium paddlewheel complexes using distinct coordination environments around each of the ruthenium centers.
本文报道了在二钌桨轮配合物中使用芳基作为轴向配体，通过金属-金属-配体相互作用来调控远端金属位点的反应活性。Ru(ap)(Ar)（ap = 2-苯胺基吡啶，Ar = CH-4-NMe）中 vacant ruthenium 位点因此具有反应活性，能够与一系列等电子配体结合，得到三种形式为(Y)Ru(ap)的配合物[Y = CN（），HC≡C（），CO（）]，每种配合物都呈现出独特的电子结构。虽然与阴离子配体的反应随后会导致二钌核心从Ru(II,III)氧化为Ru(III,III)，但与CO的反应产生了一个罕见的Ru(II,III)-CO加合物实例。后一个反应特别有趣，因为其基态从 = / 在 到 = / 在 发生了完全可逆的变化，这在Ru(II,III)物种中是首次见到。总的来说，这项工作揭示了利用每个钌中心周围不同的配位环境来调节二钌桨轮配合物电子结构的方法。 （注：原文中部分括号内容缺失具体内容，翻译时保留原样）
