Charged, but found "not guilty": innocence of the suspect bridging ligands [RO(O)CNNC(O)OR]2- = L2- in [(acac)2Ru(μ-L)Ru(acac)2]n, n = +,0,-,2-.
Charged, but found "not guilty": innocence of the suspect bridging ligands [RO(O)CNNC(O)OR]2- = L2- in [(acac)2Ru(μ-L)Ru(acac)2]n, n = +,0,-,2-.
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被指控，但被认定“无罪”：嫌疑人桥接配体 [RO(O)CNNC(O)OR]2- = L2- in [(acac)2Ru(μ-L)Ru(acac)2]n 无罪， n = ,0,-,2-
DOI：
10.1021/ic300809w
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发表时间：
2012
影响因子：
4.6
通讯作者：
W. Kaim
中科院分区：
文献类型：
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作者：
S. Roy;B. Sarkar;H.-G. Imrich;J. Fiedler;S. Záliš;R. Jimenez-Aparicio;F. A. Urbanos;S.M. Mobin;G.K. Lahiri;W. Kaim
通过Ru(Acac)2(CH3CN)2(μ-OR)与偶氮二甲酸二酯(ADC-OR)之间的电子转移反应，得到了中性的非对映异构体二Ru(Ⅲ)配合物(acac-[(Acac)2Ru(Acac)2Ru(acc-or)Ru(Acac)2])(acac-=2，4-戊二酮和adc-OR2-=二烷基偶氮二羧酸=[RO(O)CNNC(O)OR]2-，R=叔丁基或异丙基)。对R=异丙基的异构体3进行了结构表征，在N-N=1.440(5)的还原双阴离子桥上发现了两种去质子化和N-N偶联的氨基甲酸酯功能。两个氧化的、反铁磁耦合的RuII中心之间的距离相当短，为4.764？R=异丙基的手性异构体4表现出较强的反铁磁性偶联。虽然中性化合物的氧化只在3和4是完全可逆的，但两个分离良好的可逆单电子还原步骤产生了单阴离子中间体1-4-，在近红外(NIR)区域有强烈的(ε≈3000M-1 cm-1)和宽的(Δν1/2≈3000 cm-1)吸收。即使在4K也没有电子顺磁共振(EPR)信号，这有利于具有无辜桥联配体的混价形式RuII(ADC-OR2-)RuII(ADC-OR·-)RuII(ADC-OR·-)RuII，这一观点得到了甲酯模型体系金属中心自旋的支持。络合物的二次还原导致近红外吸收完全消失，EPR沉默的氧化形式3+和4+，用不对称的自旋分布计算，不表现出近红外(NIR)活性。[(Acac)2Ru(μ-adc-R)Ru(Acac)2]n(n=+，0，-，2−)，[(Bpy)2Ru(μ-adc-R)Ru(Bpy)2]k(k=4+，3+，2+，0，2−)和[(Acac)2Ru(μ-dih-R)Ru(Acac)2]m(m=2+，+，0，-，2-；DIH-R2-=1，2-二亚氨基酰肼(2-))的奇电子中间体的电子结构和同一性被比较，揭示了无辜和非无辜行为的二分法。
Neutral diastereoisomeric diruthenium(III) complexes,meso- andrac-[(acac)2Ru(μ-adc-OR)Ru(acac)2] (acac–= 2,4-pentanedionato and adc-OR2–= dialkylazodicarboxylato = [RO(O)CNNC(O)OR]2–, R =tert-butyl or isopropyl), were obtained from electron transfer reactions between Ru(acac)2(CH3CN)2and azodicarboxylic acid dialkyl esters (adc-OR). Themesoisomer3with R = isopropyl was structurally characterized, revealing two deprotonated and N–N coupled carbamate functions in a reduced dianionic bridge withdN–N= 1.440(5) Å. A rather short distance of 4.764 Å has been determined between the two oxidized, antiferromagnetically coupled RuIIIcenters. Theracisomer4with R = isopropyl exhibited stronger antiferromagnetic coupling. While the oxidation of the neutral compounds was fully reversible only for3and4, two well-separated (108<Kc< 1010) reversible one-electron reduction steps produced monoanionic intermediates1––4–with intense (ε ≈ 3000 M–1cm–1), broad (Δν1/2≈ 3000 cm–1) absorptions in the near-infrared (NIR) region around 2000 nm. The absence of electron paramagnetic resonance (EPR) signals even at 4 K favors the mixed-valent formulation RuII(adc-OR2–)RuIIIwith innocently behaving bridging ligands over the radical-bridged alternative RuII(adc-OR•–)RuII, a view which is supported by the metal-centered spin as calculated by density functional theory (DFT) for the methyl ester model system. The second reduction of the complexes causes the NIR absorption to disappear completely, the EPR silent oxidized forms3+and4+, calculated with asymmetrical spin distribution, do not exhibit near infrared (NIR) activity. The series of azo-bridged diruthenium complex redox systems [(acac)2Ru(μ-adc-R)Ru(acac)2]n(n= +,0,–,2−), [(bpy)2Ru(μ-adc-R)Ru(bpy)2]k(k= 4+,3+,2+,0,2−), and [(acac)2Ru(μ-dih-R)Ru(acac)2]m(m= 2+,+,0,–,2–; dih-R2–= 1,2-diiminoacylhydrazido(2-)) is being compared in terms of electronic structure and identity of the odd-electron intermediates, revealing the dichotomy of innocent vs noninnocent behavior.
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