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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Racemic monoperoxovanadium(V) complexes with achiral OO and ON donor set heteroligands: synthesis, crystal structure and stereochemistry of [NH3(CH2)(2)NH3][VO(O-2)(ox)(pic)]center dot 2H(2)O and [NH3(CH2)(2)NH3][VO(O-2)(ox)(pca)]
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Racemic monoperoxovanadium(V) complexes with achiral OO and ON donor set heteroligands: synthesis, crystal structure and stereochemistry of [NH3(CH2)(2)NH3][VO(O-2)(ox)(pic)]center dot 2H(2)O and [NH3(CH2)(2)NH3][VO(O-2)(ox)(pca)]

机译：具有非手性OO和供体集杂配体的外消旋单过氧钒（V）配合物：[NH3（CH2）（2）NH3] [VO（O-2）（ox）（pic）]中心点2H（的合成，晶体结构和立体化学2）O和[NH3（CH2）（2）NH3] [VO（O-2）（ox）（pca）]

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Monoperoxovanadium(V) complexes, [NH3(CH2)(2)NH3][VO(O-2)(ox)(pic)]center dot 2H(2)O (1) and [NH3(CH2)(2)NH3][VO(O-2)(ox)(pca)] (2) [NH3(CH2)(2)NH3 = ethane-1,2-diammonium(2+), ox = oxalate(2-), pic = pyridine-2-carboxylate(1-), pca = pyrazine-2-carboxylate(1-)], were synthesized and characterized by X-ray analysis, IR and Raman spectroscopies. The five equatorial positions of the pentagonal bipyramid around the vanadium atoms are occupied by the eta(2)-peroxo ligand, two oxygen atoms of the ox, and the nitrogen atom of the pic or pca ligands, respectively. The oxo ligand and the oxygen atom of pic or pca are in the axial positions. Networks of X-H center dot center dot center dot O (X= C, N or O) hydrogen bonds, and pi-pi interactions between aromatic rings in 1 and anion-pi interactions in 2, determine the molecular packings and build up the supramolecular architecture. Three stereochemical rules for occupation of the donor sites in two-heteroligand [VO(O-2)(L-1)(L-2)] complexes (L-1, L-2 are bidentate neutral or differently charged anionic heteroligands providing an OO, NN or ON donor set) are discussed. 1 and 2 crystallize as racemic compounds. The V-51 NMR spectra proved that the parent complex anions of 1 and 2 partially decompose on dissolution in water to the monoperoxo-ox, - pic or -pca complexes.
机译：单过氧钒（V）络合物，[NH3（CH2）（2）NH3] [VO（O-2）（ox）（pic）]中心点2H（2）O（1）和[NH3（CH2）（2）NH3 ] [VO（O-2）（ox）（pca）]（2）[NH3（CH2）（2）NH3 =乙烷-1,2-二铵（2+），ox =草酸盐（2-），pic =合成了吡啶-2-羧酸盐（1-），pca =吡嗪-2-羧酸盐（1-）]，并通过X射线分析，IR和拉曼光谱进行了表征。钒原子周围的五角双锥体的五个赤道位置分别被eta（2）-peroxo配体，ox的两个氧原子和pic或pca配体的氮原子占据。 pic或pca的氧代配体和氧原子位于轴向位置。 XH中心点中心点中心点O（X = C，N或O）的氢键网络以及1中的芳香环之间的pi-pi相互作用和2中的阴离子-pi相互作用决定了分子堆积并建立了超分子结构。两个杂配体[VO（O-2）（L-1）（L-2）]配合物（L-1，L-2为双齿中性或带不同电荷的阴离子杂配体）中供体位点占据的三个立体化学规则讨论了OO，NN或ON供体集。 1和2结晶为外消旋化合物。 V-51 NMR光谱证明，母体配体阴离子1和2在溶解于水中时部分分解成单过氧-ox，-pic或-pca配合物。

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