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Vicinal Dinitridoruthenium-Substituted Polyoxometalates-[XW_(10)O_(38)RuN}_2]~6(X = Si or Ge)

机译:邻氨基二恶英钌取代的多金属氧酸盐-[XW_(10)O_(38)RuN} _2]〜6(X = Si或Ge)

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摘要

Reaction of the divacantpolyox‘metalate Ks[y-XW10036] (X=Si, Ge) with two equivalents of themetal-nitrido precursor Cs2[RuvINC15],at room temperature in water, produ- cesK2(Me2NH2),H2[y-XW1503,- {RuN}2], Si (DMA-la) or Ge(DMA-lb). The X-ray crystal struc-tures of both complexes show mono-meric complexes with highly unusualvicinal terminal metal-nitrido units.The RuN bond lengths are 1.594(10)and 1.612(11) A in la and lb, respec- tively. EXAFS studies confirmed thekey structural assignments from X-raycrystallography. The XANES spectrumof DMA-la, diamagnetism, NMR (29Siand 153W) chemical shifts, voltammetricbehavior, reductive titrations with [PW1204014 5 and computational data are all consistent with d2 Ruvl centers in these complexes. The FT-IR andRaman spectra show the expected vi-brational modes of the {y-XWI0) unitand the Ru-N stretch at 1080 cm-1, re-spectively. Interestingly, reduction ofDMA-la by 4 equivalents of[PW12O40]4- produces NH3 in nearlyquantitative yield. Cyclic voltammetryversus pH and calculations provide theenergetics for the possible two-electronreduction and two-proton addition pro-cesses in this reaction.
机译:在室温下,水中的二空多氧合金属氧化物Ks [y-XW10036](X = Si,Ge)与两当量的金属-氮化物前体Cs2 [RuvINC15]反应,产物K2(Me2NH2),H2 [y-XW1503 ,-{RuN} 2],Si(DMA-1a)或Ge(DMA-1b)。两种配合物的X射线晶体结构均显示具有高度不寻常的末端金属-氮化物单元的单体配合物。RuN键长分别为la和lb的1.594(10)和1.612(11)A。 EXAFS研究证实了X射线晶体学的关键结构任务。 DMA-1a的XANES光谱,抗磁性,NMR(29Si和153W)化学位移,伏安行为,用[PW1204014 5的还原滴定和计算数据都与这些配合物中的d2 Ruvl中心一致。 FT-IR和拉曼光谱分别显示了(y-XWI0)单元的预期振动模式和Ru-N在1080 cm-1处的拉伸。有趣的是,将DMA-1a还原为4当量的[PW12O40] 4-会产生接近定量的NH3。循环伏安法与pH值的比较和计算为该反应中可能的两电子还原和两质子加成过程提供了能量学。

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