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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The structural mobility of zinc complexes with tetradentate tripodal ligands derived from the amino acids glycine and phenylalanine
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The structural mobility of zinc complexes with tetradentate tripodal ligands derived from the amino acids glycine and phenylalanine

机译：锌结构与四齿三脚形配体衍生自氨基酸甘氨酸和苯丙氨酸的结构迁移率

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摘要

Crystallographic studies indicate that aromatic interactions favor the formation of trigonal-bipyramidal zinc(II) complexes with the tetradentate tripodal ligand bpaAc-Phe-OMe (N,N-bis(2-picolyl)aminoacyl-(S)-phenylalanine-methylester).The benzyl side chain in [(bpaAc-Phe-OMe)Zn(OTf)]~+ (1b,OTf=triflate),[(bpaAc-Phe-OMe)Zn-(H_2O)]~(2+) (2b) and [(bpaAc-Phe-OMe)Zn(pz)]~(2+) (3b~t,pz=pyrazole; t=trigonal-bipyramidal) is oriented towards the axial active coordination site with the phenyl ring ca.4.5 A away from the metal center.Here we show that this conformation is retained in solutions of 1b,2b and [(bpaAc-Phe-OMe)Zn(Cl)]~+ (8b).Temperature-dependent ~1H NMR spectra reveal that the phenylalanine side chain is locked in its position as long as the coordination sphere stays trigonal-bipyramidal.Based on our Crystallographic results we expected the pyrazole and N-methylimidazole complexes 3b~t and [(bpaAc-Phe-OMe)Zn(N-Meim)]~(2+) (4b~t,N-Meim=N-methylimidazole) to be labile with respect to addition of a sixth ligand such as triflate,water,pyrazole or N-methylimidazole.~1H NMR studies confirm that the six-coordinate species 3bdeg and 4bdeg (o: octahedral) are formed in solution.This is presumably due to solvation effects and mobilizes the benzyl side chain which is flexible in octahedral complexes.
机译：晶体学研究表明，芳香族相互作用有利于与四齿三脚架配体bpaAc-Phe-OMe（N，N-双（2-picolyl）氨基酰基-（S）-苯丙氨酸-甲基酯）形成三角-双锥体锌（II）络合物。 [（bpaAc-Phe-OMe）Zn（OTf）]〜+（1b，OTf = triflate），[（bpaAc-Phe-OMe）Zn-（H_2O）]〜（2+）（2b）中的苄基侧链和[（bpaAc-Phe-OMe）Zn（pz）]〜（2+）（3b〜t，pz =吡唑; t =三角双锥体）朝向带有苯环约4.5 A的轴向活性配位点在这里，我们证明此构象保留在1b，2b和[（bpaAc-Phe-OMe）Zn（Cl）]〜+（8b）的溶液中。温度相关的〜1H NMR光谱表明只要配位球保持三角双锥体，苯丙氨酸侧链就被锁定在其位置。根据我们的晶体学结果，我们预期吡唑和N-甲基咪唑复合物3b〜t和[（bpaAc-Phe-OMe）Zn（N-Meim ）]〜（2+）（4b〜t，N-Meim = N-甲基咪唑）关于1F NMR研究证实六配位物质3bdeg和4bdeg（o：八面体）是在溶液中形成的，这大概是由于溶剂化效应并能移动在八面体络合物中具有柔性的苄基侧链。

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