Vanadium(V) Oxyanions. Interactions of Vanadate with Cyclic Diols and Monosaccharides
Vanadium(V) Oxyanions. Interactions of Vanadate with Cyclic Diols and Monosaccharides
复制标题
钒(V) 氧阴离子。
DOI：
10.1002/chin.198847248
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发表时间：
1988
期刊：
影响因子：
--
通讯作者：
M. Gresser
中科院分区：
文献类型：
--
作者：
A. Tracey;M. Gresser
结论特征性的超卟啉光谱特征，出现在双（硫醇基）连接到Rhm（OEP）Cl时，显示出与P-450 cam、钴取代的P-450 cam和双（硫醇基）-Fem（TPP）、-Com（TPP）和-Crm（TPP）复合物的硫醇基加合物所观察到的那些特征显著相似。双-含有各种类型的脂肪族和芳香族硫醇化合物的（硫醇合）-Rhm（OEP）络合物在室温下在空气中是稳定的，其特征Soret分裂带的位置与醇类溶剂的介电常数及苯硫酚衍生物轴向配体取代基的Hammett a值呈线性相关在丙酮和苯溶剂中。具有4d和5d电子的金属卟啉的不寻常的HP光谱已经为锑（III）和铋（III）卟啉所知。然而，由于具有4d电子的双（硫醇基）金属卟啉形成配位模式，本发明的双（硫醇基）-RhUI（OEP）配合物是HP光谱的第一个实例。在观察到的形成超卟啉光谱的条件下，在77 K下通过ESR光谱法可检测到游离超氧阴离子的产生。在此基础上，提出了双（硫醇根）-Rhni-（OEP）配合物产生超氧阴离子的可能反应机理。
Conclusion. Characteristic hyperporphyrin spectral features that appear upon bis (thiolato) ligation to Rhm (OEP) Cl showed a marked similarity to those observed for thiolato adducts of P-450cam, cobalt-substituted P-450cam, and bis (thiolato)-Fem (TPP),-Com (TPP), and-Crm (TPP) complexes. The bis-(thiolato)-Rhm (OEP) complexes containing various types of aliphatic and aromaticthiol compounds were stable at room temperature under air, their half-lives being over 30 min. The positions of the characteristic split Soret band correlated linearly with the dielectric constants of alcohols as solvent and with the Hammett a values of the substituents of thiophenol derivatives as axial ligands on Rhni (OEP) in both acetone and benzene solvents. The unusual HP spectra with metalloporphyrinshaving 4d and 5d electrons are already known for antimony (III) and bismuth (III) porphyrins. 3 4® However, the present bis (thiolato)-RhUI (OEP) complex is the first example for HP spectra due to the formationof the coordination mode by bis (thiolato) metalloporphyrins having 4d electrons. Under the conditions observed for the formation of a hyperporphyrin spectrum, the generation of free superoxide anion was detectable at 77 K by ESR spec-trometry. On the basis of the results, a possible reaction mechanism generating the superoxide anion by a bis (thiolato)-Rhni-(OEP) complex is proposed.