基于N-水杨醛-o-氨基酚及其衍生物的单核阴离子八面体钴(III)配合物：合成、结构与光谱研究

Mononuclear anionic octahedral cobalt(III) complexes based on N-salicylidene-o-aminophenol and its derivatives: synthetic, structural and spectroscopic studies.

作者信息

Alexopoulou Konstantina I, Zagoraiou Eirini, Zafiropoulos Theodoros F, Raptopoulou Catherine P, Psycharis Vassilis, Terzis Aris, Perlepes Spyros P

机构信息

Department of Chemistry, University of Patras, GR-265 04 Patras, Greece.

Department of Materials Science, Institute of Advanced Materials, Physicochemical Processes, Nanotechnology and Microsystems, NCSR "Demokritos", GR-153 10 Aghia Paraskevi Attikis, Greece.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2015 Feb 5;136 Pt A:122-30. doi: 10.1016/j.saa.2013.11.024. Epub 2013 Nov 16.

DOI:10.1016/j.saa.2013.11.024

PMID:24315445

Abstract

The reactions of Co(II) sources with N-salicylidene-o-aminophenol (H2saph), N-salicylidene-o-amino-4-methylphenol (H2saph-4Me) and N-salicylidene-o-amino-4-chlorophenol (H2saph-4Cl) were studied in MeOH. The new solid complexes (Bu4(n)N)[Co(III)(saph)2] (1), (Et3NH)[Co(III)(saph-4Me)2]⋅MeOH⋅MeCO2H (2⋅MeOH⋅MeCO2H) and (Et3NH)[Co(III)(saph-4Cl)2]⋅MeOH⋅MeCO2H (3⋅MeOH⋅MeCO2H) have been isolated and their structures determined by single-crystal, X-ray crystallography. The three compounds contain the mononuclear, low- spin octahedral anion Co(III)L2 (H2L=H2saph, H2saph-4Me, H2saph-4Cl), in which both L(2)(-) ligands act as tridentate chelating, meridional ONO donors. The crystal structures of 2⋅MeOH⋅MeCO2H and 3⋅MeOH⋅MeCO2H are built through H-bonding and π-π stacking interactions. The new complexes were characterized by elemental analyses and spectroscopic (IR, Raman, UV/VIS, (1)H NMR) data. All data are discussed in terms of the nature of bonding and known structures.

摘要

研究了Co(II)源与N-水杨醛基邻氨基酚（H2saph）、N-水杨醛基邻氨基-4-甲基苯酚（H2saph-4Me）和N-水杨醛基邻氨基-4-氯苯酚（H2saph-4Cl）在甲醇中的反应。分离得到了新的固体配合物（Bu4(n)N）[Co(III)(saph)2]（1）、（Et3NH）[Co(III)(saph-4Me)2]⋅MeOH⋅MeCO2H（2⋅MeOH⋅MeCO2H）和（Et3NH）[Co(III)(saph-4Cl)2]⋅MeOH⋅MeCO2H（3⋅MeOH⋅MeCO2H），并通过单晶X射线晶体学确定了它们的结构。这三种化合物都含有单核、低自旋八面体阴离子Co(III)L2（H2L = H2saph、H2saph-4Me、H2saph-4Cl），其中两个L(2)(-)配体均作为三齿螯合、经式ONO供体。2⋅MeOH⋅MeCO2H和3⋅MeOH⋅MeCO2H的晶体结构通过氢键和π-π堆积相互作用构建而成。通过元素分析和光谱（红外、拉曼、紫外/可见、(1)H NMR）数据对新配合物进行了表征。所有数据均根据键合性质和已知结构进行了讨论。