Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] Towards the "Naked" Cations Cu(+) , Ag(+) , and Tl(.).
Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] Towards the "Naked" Cations Cu(+) , Ag(+) , and Tl(.).
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DOI：
10.1002/anie.201506362
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发表时间：
2015-10-26
期刊：
影响因子：
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通讯作者：
Scheer M
中科院分区：
文献类型：
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作者：
Fleischmann M;Dielmann F;Gregoriades LJ;Peresypkina EV;Virovets AV;Huber S;Timoshkin AY;Balázs G;Scheer M
环- p6配合物[(Cp*Mo)2(μ,η6:η6- p6)](1)早在30年前就有报道，但对其化学性质知之甚少。在这里，我们报道了1的高产合成，配合物2，包含一个前所未有的环p10配体，以及1对“裸”阳离子Cu+， Ag+和Tl+的反应性。除了形成具有双烯基扭曲环- p6中间层的单一氧化产物3a，b外，还描述了具有扭曲方平面(M=Cu（4a), Ag(4b)）或扭曲四面体配位（M=Cu(5)） M+阳离子的[M(1)2]+配合物。通过粉末XRD和DFT计算证实，溶剂的选择可以控制Cu+的反应结果。与Tl+的反应在固体状态下形成了层状的二维配位网络。
Although the cyclo-P6 complex [(Cp*Mo)2(μ,η6:η6-P6)] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the “naked” cations Cu+, Ag+, and Tl+. Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2]+ complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M+ cations. The choice of solvent enabled control over the reaction outcome for Cu+, as proved by powder XRD and supported by DFT calculations. The reaction with Tl+ affords a layered two-dimensional coordination network in the solid state.