Mononuclear Ca(II)-bulky aryl-phosphate monoanion and dianion complexes with ortho-amide groups.
Mononuclear Ca(II)-bulky aryl-phosphate monoanion and dianion complexes with ortho-amide groups.
复制标题
具有邻酰胺基团的单核 Ca(II)-大体积芳基磷酸一价阴离子和二价阴离子络合物。
DOI：
10.1021/ic010570f
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发表时间：
2002
影响因子：
4.6
通讯作者：
N. Ueyama
中科院分区：
文献类型：
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作者：
A. Onoda;Yusuke Yamada;T. Okamura;Hitoshi Yamamoto;N. Ueyama
两个新的单核钙（II）配合物与芳基磷酸二氢盐配体具有两个战略取向的庞大的酰胺基团，2，6-（Ph 3CCONH）2C 6 H3 OPO 3 H2（1），包括具有磷酸盐单阴离子的一种，（NMe 4）[CaII[O2 P（OH）OC 6 H3 - 2，6-（NHCOCPh 3）2]3（NCMe）3]（3），和一种具有磷酸根二价阴离子[CaII[O3 POC 6 H3 - 2，6-（NHCOCPh 3）2]（H2O）3（MeOH）2]（4）。两者都是NH的类似物。含Ca（II）磷酸转移酶活性中心的O氢键。晶体学研究表明，酰胺基的NH键是指向磷酸根的未配位氧原子的，IR和1HNMR谱表明，强NH键是指向磷酸根的未配位氧原子的。O氢键仅在磷酸盐二价阴离子状态下形成。3与一个非氢键磷酸配体的配体交换反应表明，NH +4是一个配体。O氢键阻止了Ca-O键的解离。比较Ca-O键的距离与Ca-O-P角的散点图分析、傅立叶密度分析和DFT计算揭示了Ca-O（磷酸盐）键中存在部分程度的共价性。
Two new mononuclear Ca(II) complexes with aryl dihydrogen phosphate ligands having two strategically oriented bulky amide groups, 2,6-(Ph3CCONH)2C6H3OPO3H2 (1), including one with a phosphate monoanion, (NMe4)[CaII[O2P(OH)OC6H3-2,6-(NHCOCPh3)2]3(NCMe)3] (3), and one with a phosphate dianion, [CaII[O3POC6H3-2,6-(NHCOCPh3)2](H2O)3(MeOH)2] (4). Both are analogues for the NH...O hydrogen bonds in the active site of Ca(II)-containing phosphotransferase. Crystallographic studies of these Ca(II) complexes revealed that the amide NHs are directed to uncoordinated O atoms of the phosphates, and the IR and 1H NMR spectra indicate that strong NH...O hydrogen bonds are formed only in the phosphate dianion state. The ligand exchange reaction of 3 with a non-hydrogen-bonded phosphate ligand shows that the NH...O hydrogen bonds prevent the Ca-O bond from dissociation. A scatter plot analysis comparing the distance of a Ca-O bond with the Ca-O-P angle, the Fourier density analysis, and DFT calculations reveal that a partial degree of covalency in the Ca-O(phosphate) bonds is present.