含第15族金属离子的咕啉。含处于+3、+4氧化态的砷、锑和铋离子的八乙基咕啉的合成与表征。

Corroles with group 15 metal ions. Synthesis and characterization of octaethylcorroles containing As, Sb, and Bi ions in +3, +4, and oxidation states.

作者信息

Kadish K M, Erben C, Ou Z, Adamian V A, Will S, Vogel E

机构信息

Department of Chemistry, University of Houston, Houston, Texas 77204-5641, USA.

出版信息

Inorg Chem. 2000 Jul 24;39(15):3312-9. doi: 10.1021/ic991361m.

DOI:10.1021/ic991361m

PMID:11196869

Abstract

The synthesis, spectroscopic characterization, and electrochemistry of As, Sb, and Bi corroles are reported. The investigated complexes are represented by [(OEC)AsV(CH3)]+ClO4- and (OEC)M where M = As(III), Sb(III), or Bi(III) and OEC is the trianion of octaethylcorrole. The products of each redox reaction are characterized by UV-vis and ESR spectroscopy. The first one-electron oxidations of (OEC)As and (OEC)Sb are metal-centered and result in the formation of [(OEC)AsIV]+ and [(OEC)SbIV]+. A second one-electron oxidations generates [(OEC)AsV]2+ and [(OEC.)SbIV]2+, the latter of which is slowly converted to a Sb(V) corrole, [(OEC)SbV]2+. The first one-electron oxidation of (OEC)Bi leads only to the Bi(III) pi-cation radical, but a second one-electron oxidation is proposed to give a Bi(IV) complex, [(OEC)Bi]2+. The first reduction of [(OEC)AsV(CH3)]+ClO4- is accompanied by loss of the sigma-bonded methyl ligand and formation of an As(III) complex.

摘要

报道了砷、锑和铋卟吩的合成、光谱表征及电化学性质。所研究的配合物由[(OEC)AsV(CH3)]+ClO4-和(OEC)M表示，其中M = As(III)、Sb(III)或Bi(III)，OEC为八乙基卟吩的三价阴离子。每个氧化还原反应的产物通过紫外可见光谱和电子自旋共振光谱进行表征。(OEC)As和(OEC)Sb的首次单电子氧化是以金属为中心的，生成[(OEC)AsIV]+和[(OEC)SbIV]+。第二次单电子氧化生成[(OEC)AsV]2+和[(OEC.)SbIV]2+，后者缓慢转化为锑(V)卟吩[(OEC)SbV]2+。(OEC)Bi的首次单电子氧化仅生成Bi(III) π-阳离子自由基，但第二次单电子氧化预计会生成Bi(IV)配合物[(OEC)Bi]2+。[(OEC)AsV(CH3)]+ClO4-的首次还原伴随着σ键合甲基配体的损失并形成As(III)配合物。