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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and mixed valence aspects of [{(L)ClRu}_2(μ-tppz)]~(n+) incorporating 2, 2'-dipyridylamine (L) as ancillary and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) as bridging ligand
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Synthesis and mixed valence aspects of [{(L)ClRu}_2(μ-tppz)]~(n+) incorporating 2, 2'-dipyridylamine (L) as ancillary and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) as bridging ligand

机译:[{(L)ClRu} _2(μ-tppz)]〜(n +)的合成和混合价方面,其中包含2,2'-联吡啶胺(L)作为辅助和2,3,5,6-四(2-吡啶基)吡嗪(tppz)作为桥联配体

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摘要

The tppz-bridged diruthenium complex [{(L)ClRu~(ii)}_2(μ-tppz)](ClO_4)_2, [1](ClO_4)_2 {tppz = 2,3,5,6-tetrakis(2-pyridyl)-pyrazine, L = 2,2'-dipyridylamine} and its mononuclear counterpart [(L)ClRu~(ii)(tppz)]ClO_4, [2](ClO_4) have been synthesized. The 380 mV separation between successive Ru~(ii)/Ru~(iii) couples in [1]~(2+) leads to a comproportionation constant (K_c) of 2.7 * 10~6. Consequently, the Ru~(ii)Ru~(iii) species [1]~(3+) exhibits a rather narrow intervalence charge transfer band at 1700 nm, suggesting a class III mixed-valence state, the electronic coupling constant (V_(ab)) is calculated at 2940 cm~(-1). Complex [1]~(3+) displays a rhombic EPR spectrum at 4 K (g_1 = 3.390, g_2 = 2.278, g_3 = 1.697), characteristic of ruthenium(iii) in a distorted octahedral environment. Both complexes show two successive tppz-based reduction processes [(tppz)~(0/-1) and (tppz)~(-1/-2)]. The one-electron reduced species [1]~+ is a tppz radical anion species with an intense low-energy band at 1105 nm and an axial EPR signal at 4 K (g_1 = 2.008, g_2 = g_3 = 1.994). [1]~(2+) and [2]~+ exhibit moderately strong emissions at 740 nm and 668 nm, respectively, in EtOH-MeOH glass at 77K.
机译:tppz桥联的钌络合物[{(L)ClRu〜(ii)} _ 2(μ-tppz)](ClO_4)_2,[1](ClO_4)_2 {tppz = 2,3,5,6-tetrakis(2 -吡啶基)-吡嗪,L = 2,2′-二吡啶胺}及其单核对应物[(L)ClRu-(ii)(tppz)] ClO_4,[2](ClO_4)。 [1]〜(2+)中连续的Ru〜(ii)/ Ru〜(iii)对之间的380 mV间隔导致了2.7 * 10〜6的相称常数(K_c)。因此,Ru〜(ii)Ru〜(iii)种类[1]〜(3+)在1700 nm处显示出较窄的间隔电荷转移带,表明III类混合价态,即电子耦合常数(V_( ab))计算为2940 cm〜(-1)。络合物[1]〜(3+)在扭曲的八面体环境中显示了钌(iii)的特征,在4 K处具有菱形EPR谱(g_1 = 3.390,g_2 = 2.278,g_3 = 1.697)。两种络合物均显示两个连续的基于tppz的还原过程[(tppz)〜(0 / -1)和(tppz)〜(-1 / -2)]。单电子还原物种[1]〜+是一种tppz自由基阴离子物种,在1105 nm处具有很强的低能带,在4 K处具有轴向EPR信号(g_1 = 2.008,g_2 = g_3 = 1.994)。在77K的EtOH-MeOH玻璃中,[1]〜(2+)和[2]〜+分别在740 nm和668 nm处显示中等强度的发射。

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