1,2-双（芳基亚氨基）苊烯（芳基-BIAN）配体对磷（I）和砷（I）部分的捕获。分子内电荷转移的一个实例。

Capture of phosphorus(I) and arsenic(I) moieties by a 1,2-bis(arylimino)acenaphthene (aryl-BIAN) ligand. A case of intramolecular charge transfer.

作者信息

Reeske Gregor, Hoberg Clint R, Hill Nicholas J, Cowley Alan H

机构信息

Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165, USA.

出版信息

J Am Chem Soc. 2006 Mar 8;128(9):2800-1. doi: 10.1021/ja058459m.

DOI:10.1021/ja058459m

PMID:16506749

Abstract

The reaction of PCl3 with SnCl2 in THF solution, followed by treatment with dpp-BIAN (dpp = 2,6-i-Pr2C6H3), affords the phosphenium complex [(dpp-BIAN)P][SnCl5.THF]. The 31P chemical shift (delta 232.5) and the metrical parameters from a single-crystal X-ray diffraction study indicate that the oxidation state of phosphorus in this compound is +3. A similar conclusion was reached regarding the phosphorus oxidation state in [(dpp-BIAN)P][I3], which was prepared via the reaction of dpp-BIAN with PI3 in CH2Cl2 solution. The arsenium salt [(dpp-BIAN)As][SnCl5.THF] was prepared by treatment of AsCl3 with SnCl2 in THF solution, followed by the addition of dpp-BIAN. The X-ray crystal structure of this salt was determined, and the pattern of bond distances and angles indicates that arsenic is present in the +3 oxidation state.

摘要

在四氢呋喃（THF）溶液中，三氯化磷（PCl₃）与二氯化锡（SnCl₂）反应，随后用二（2,6 - 二异丙基苯基）胺（dpp - BIAN，dpp = 2,6 - 二异丙基苯基）处理，得到鏻配合物[(dpp - BIAN)P][SnCl₅·THF]。³¹P化学位移（δ 232.5）以及单晶X射线衍射研究得到的测量参数表明，该化合物中磷的氧化态为 +3。通过dpp - BIAN与三碘化磷（PI₃）在二氯甲烷（CH₂Cl₂）溶液中反应制备的[(dpp - BIAN)P][I₃]中磷的氧化态也得出了类似结论。通过在四氢呋喃溶液中用二氯化锡处理三氯化砷（AsCl₃），随后加入dpp - BIAN，制备了砷盐[(dpp - BIAN)As][SnCl₅·THF]。测定了该盐的X射线晶体结构，键长和键角模式表明砷以 +3氧化态存在。