Bera Sachinath, Maity Suvendu, Weyhermüller Thomas, Ghosh Prasanta
Department of Chemistry, R. K. Mission Residential College, Narendrapur, Kolkata-103, India.
Max-Planck-Institut für Chemische Energiekonversion, Stiftstrasse 34-36, D-45470 Mülheim, Germany.
Dalton Trans. 2016 May 10;45(19):8236-47. doi: 10.1039/c6dt00091f.
9,10-Phenanthreneiminosemiquinonate anion radical (PIQ˙(-)) complexes of ruthenium of types trans-[Ru(II)(PIQ˙(-))(PPh3)2(CO)Cl] () and trans-[Ru(III)(PIQ˙(-))(PPh3)2Cl2] () are reported. Reactions of and with I2 afford trans-Ru(III)(PIQ˙(-))(PPh3)2(CO)ClI3(-)·½CH2Cl2 ((+)I3(-)·½CH2Cl2) and trans-Ru(PIQ˙(-))2(PPh3)2(μ-Cl)3I3(-)·¼I2·¼toluene) ((+)I3(-)·¼I2·¼toluene), while the reaction of with Br2 yields a 9,10-phenanthreneiminoquinone (PIQ) complex of the type mer-[Ru(III)(PIQ)(PPh3)Br3]·½CH2Cl2 (·½CH2Cl2). In comparison, the reaction of trans-[Ru(III)(PQ˙(-))(PPh3)2Cl2] (PQ), a 9,10-phenanthrenequinone (PQ) analogue of affords only trans-Ru(III)(PQ)(PPh3)2Cl2Br3(-) ((+)Br3(-)). Considering the X-ray bond parameters, EPR spectra and the atomic spin densities obtained from the density functional theory (DFT) calculations, is defined as a PIQ˙(-) (average C-O/N and C-C lengths, 1.280(2) and 1.453(3) Å) complex of ruthenium(ii) while is a neutral PIQ (average C-O, C-N, C-C and C-O/N lengths, 1.248(7), 1.284(7), 1.485(8) and 1.266(7) Å) complex of the ruthenium(iii) ion. The single crystal X-ray bond parameters proposed that (+)I3(-) (average C-O/N and C-C lengths, 1.294(8) and 1.449(9) Å) and (average C-O/N and C-C lengths, 1.289(2) and 1.447(4) Å) are PIQ˙(-) complexes of ruthenium(iii), while the (+) ion (average C-O/N and C-C lengths, 1.288 ± 0.004 and 1.450 ± 0.017 Å) is a co-facial bi-octahedral complex of ruthenium(iii). In contrast, the (+) ion is a PQ complex of the ruthenium(iii) ion. EPR spectra and the calculated atomic spin densities authenticated that the (+) ion obtained after constant potential coulometric oxidation of is a PIQ complex of ruthenium(iii), while the (-) ion is a hybrid state of [Ru(II)(PIQ˙(-))] and [Ru(III)(PIQ(2-))] states. It is observed that the PIQ˙(-) state in which spin is more localized on the nitrogen (∼38% in and ∼35% in (-) ion) is stable and the coordination of the PIQ(2-) state is not observed in this study. Redox activities, UV-vis/NIR absorption spectra and their origins and the spectroelectrochemical measurements for → (+), → (-) and (+) → (2+) conversions are analyzed.
报道了反式-Ru(II)(9,10 - 菲咯啉亚胺半醌阴离子自由基(PIQ˙(-))(三苯基膦)2(CO)Cl和反式-Ru(III)(PIQ˙(-))(三苯基膦)2Cl2类型的钌的9,10 - 菲咯啉亚胺半醌阴离子自由基(PIQ˙(-))配合物。和与I2的反应生成反式-Ru(III)(PIQ˙(-))(三苯基膦)2(CO)ClI3(-)·½二氯甲烷((+)I3(-)·½二氯甲烷)和反式-Ru(PIQ˙(-))2(三苯基膦)2(μ - Cl)3I3(-)·¼I2·¼甲苯)((+)I3(-)·¼I2·¼甲苯)，而与Br2的反应生成一种mer - [Ru(III)(PIQ)(三苯基膦)Br3]·½二氯甲烷(·½二氯甲烷)类型的9,10 - 菲咯啉亚胺醌(PIQ)配合物。相比之下，反式-Ru(III)(9,10 - 菲咯啉醌阴离子自由基(PQ˙(-))(三苯基膦)2Cl2，一种9,10 - 菲咯啉醌(PQ)类似物，与Br2的反应仅生成反式-Ru(III)(PQ)(三苯基膦)2Cl2Br3(-)((+)Br3(-))。考虑到X射线键参数、电子顺磁共振(EPR)光谱以及从密度泛函理论(DFT)计算得到的原子自旋密度，被定义为钌(ii)的PIQ˙(-)(平均C - O/N和C - C长度分别为1.280(2)和1.453(3) Å)配合物，而则是钌(iii)离子的中性PIQ(平均C - O、C - N、C - C和C - O/N长度分别为1.248(7)、1.284(7)、1.485(8)和1.266(7) Å)配合物。单晶X射线键参数表明(+)I3(-)(平均C - O/N和C - C长度分别为1.294(8)和1.449(9) Å)和(平均C - O/N和C - C长度分别为1.289(2)和1.447(4) Å)是钌(iii)的PIQ˙(-)配合物，而(+)离子(平均C - O/N和C - C长度分别为1.288 ± 0.004和1.450 ± 0.017 Å)是钌(iii)的共面双八面体配合物。相比之下(+)离子是钌(iii)离子的PQ配合物。EPR光谱和计算得到的原子自旋密度证实，经恒电位库仑氧化后得到的(+)离子是钌(iii)的PIQ配合物，而(-)离子是[Ru(II)(PIQ˙(-))]和[Ru(III)(PIQ(2 - ))]状态的混合态。观察到自旋更多地定域在氮上的PIQ˙(-)状态(在中约为38%，在(-)离子中约为35%)是稳定的，并且在本研究中未观察到PIQ(2 - )状态的配位情况。分析了氧化还原活性、紫外 - 可见/近红外吸收光谱及其起源以及对于→(+)、→(-)和(+)→(2+)转化的光谱电化学测量。
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