A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands

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	A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands
	Yu, Xian-Yong ; Deng, Lin ; Zheng, Baishu ; Zeng, Bi-Rong ; Yi, Pinggui ; Xu, Xin ; Yu XY(于贤勇) ; Ceng BR(曾碧榕) ; Xu X(徐昕)
刊名	http://dx.doi.org/10.1039/c3dt51986d
	2014
关键词	HISTIDINE-LIKE LIGANDS CRYSTAL-STRUCTURE VANADIUM HALOPEROXIDASE PEROXOVANADIUM(V) COMPLEXES DIPEROXOVANADATE COMPLEXES METAL-IONS SPECIATION REACTIVITY NMR MIMICKING
英文摘要	NSF of China [21172066, 21201062, 51103122]; Ministry of Science and Technology [2011CB808505]; Scientific Research Fund of Hunan Provincial Education Department [12K101]; Hunan Provincial Natural Science Foundation of China [11JJ2007]; State Key Laboratory of Physical Chemistry of Solid Surfaces (Xiamen University) [201309]; Aid Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province; In order to understand the substitution effects of pyrazolylpyridine (pzpy) on the coordination reaction equilibria, the interactions between a series of pzpy-like ligands and biperoxidovanadate ([OV(O-2)(2)(D2O)](-)/[OV(O-2)(2)(HOD)](-), abbrv. bpV) have been explored using a combination of multinuclear (H-1, C-13, and V-51) magnetic resonance, heteronuclear single quantum coherence (HSQC), and variable temperature NMR in a 0.15 mol L-1 NaCl D2O solution that mimics the physiological conditions. Both the direct NMR data and the equilibrium constants are reported for the first time. A series of new hepta-coordinated peroxidovanadate species [OV(O-2)(2)L](-) (L = pzpy-like chelating ligands) are formed due to several competitive coordination interactions. According to the equilibrium constants for products between bpV and the pzpy-like ligands, the relative affinity of the ligands is found to be pzpy >2-Ester-pzpy approximate to 2-Me-pzpy approximate to 2-Amide-pzpy > 2-Et-pzpy. In the interaction system between bpV and pzpy, a pair of isomers (Isomers A and B) are observed in aqueous solution, which are attributed to different types of coordination modes between the metal center and the ligands, while the crystal structure of NH4[OV(O-2)(2)(pzpy)]center dot 6H(2)O (CCDC 898554) has the same coordination structure as Isomer A (the main product for pzpy). For the N-substituted ligands, however, Isomer A or B type complexes can also be observed in solution but the molar ratios of the isomer are reversed (i.e., Isomer B type is the main product). These results demonstrate that when the N atom in the pyrazole ring has a substitution group, hydrogen bonding (from the H atom in the pyrazole ring), the steric effect (from alkyl) and the solvation effect (from the ester or amide group) can jointly affect the coordination reaction equilibrium.
语种	英语
出版者	ROYAL SOC CHEMISTRY
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/92104]
专题	物理技术－已发表论文
推荐引用方式 GB/T 7714	Yu, Xian-Yong,Deng, Lin,Zheng, Baishu,et al. A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands[J]. http://dx.doi.org/10.1039/c3dt51986d,2014.
APA	Yu, Xian-Yong.,Deng, Lin.,Zheng, Baishu.,Zeng, Bi-Rong.,Yi, Pinggui.,...&徐昕.(2014).A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands.http://dx.doi.org/10.1039/c3dt51986d.
MLA	Yu, Xian-Yong,et al."A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands".http://dx.doi.org/10.1039/c3dt51986d (2014).