Synthesis, structures, optical and electrochemical properties, and complexation of 2,5-bis(pyrrol-2-yl)phospholes

被引:18
|
作者
Matano, Yoshihiro [1 ]
Fujita, Masato [1 ]
Saito, Arihiro [1 ]
Imahori, Hiroshi [1 ,2 ,3 ]
机构
[1] Kyoto Univ, Dept Mol Engn, Grad Sch Engn, Nishikyo Ku, Kyoto 6158510, Japan
[2] Kyoto Univ, Inst Integrated Cell Mat Sci iCeMS, Nishikyo Ku, Kyoto 6158510, Japan
[3] Kyoto Univ, Fukui Inst Fundamental Chem, Sakyo Ku, Kyoto 6068103, Japan
关键词
Phosphorus heterocycles; Nitrogen heterocycles; Metallacycles; Gold; Platinum; PI-CONJUGATED SYSTEMS; MOLECULAR-ORBITAL METHODS; CONVENIENT METHOD; BASIS-SETS; OLIGOMERS; CHEMISTRY; LIGANDS; ACCESS; ROUTE; PHOSPHOLES;
D O I
10.1016/j.crci.2010.03.017
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
2,5-Bis(pyrrol-2-yl)phosphole derivatives were prepared using the reaction of titanacycles, generated in situ from a Ti-II reagent and pyrrole-capped 1,6-heptadiynes, with dichloro(phenyl)phosphine. The 2,5-bis(pyrrol-2-yl)phosphole derivatives were found to possess narrower optical HOMO-LUMO gaps and less positive oxidation potentials than those of previously reported 2,5-diarylphosphole analogs. This demonstrates that the intrinsic nature of the electron excessive pyrrole subunits as well as the effective pi-conjugation over the coplanar heterole rings. The sigma(3)-P type 2,5-bis(5-phenylpyrrol-2-yl)phosphole underwent complexation with AuCl(SMe2) and PtCl2 to yield the respective AuCl-monophosphine and PtCl2-bisphosphine complexes. In the square planar Pt-II complex, the pyrrolic NH protons were found to form intramolecular hydrogen bonds with the chlorine atoms that gave rise to symmetrically split, parallel pi-chromophores linked by two Pt-P bonds. Density functional theory calculations on a Pt-II model complex suggested that this cooperative interaction induces a significant split of the original LUMOs of the symmetrical pi-conjugated ligands. (C) 2010 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
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页码:1035 / 1047
页数:13
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