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首页> 外文期刊>Chemistry: A European journal >Geminally Diaurated Aryls Bridged by Semirigid Phosphine Pillars: Syntheses and Electronic Structure
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Geminally Diaurated Aryls Bridged by Semirigid Phosphine Pillars: Syntheses and Electronic Structure

机译：半刚性磷化氢骨架桥接的双渗氮芳基化合物：合成与电子结构

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摘要

Geminally diaurated mu(2)-aryl complexes have been prepared where gold(I) centers were bridged by the semirigid diphosphine ligands bis(2-diphenylphosphinophenyl)ether (DPEphos) and 4,6-bis(diphenylphosphanyl) dibenzo[b, d] furan (DBFphos). Diaurated complexes were synthesized in ligand redistribution reactions of the corresponding di-gold dichlorides with di-gold diaryls (six of them new) and silver(I) salts. Diaurated complexes were isolated as salts of the minimally coordinating anions SbF6- and ReO4-. Efforts to prepare salts of the tetraarylborate [B(3,5-(CF3)(2)C6H3)(4)](-) led to transmetalation from boron, with crystallization of the fluorinated aryl complex. The new complexes were characterized by multinuclear NMR, absorption and emission spectroscopies, 77 K emission lifetimes, and by combustion analysis; three are crystallographically characterized. Structures of geminally diaurated aryl ligands are compared to those of mono-aurated analogues. Both crystal structures and density-functional theory calculations indicate slight but observable disruptions of aryl ligand aromaticity by geminal di-gold binding. An intermolecular aurophilic interaction in one structurally authenticated complex was examined computationally.
机译：制备了具有双缩氨基的mu（2）-芳基络合物，其中金（I）中心被半刚性二膦配体双（2-二苯基膦基苯基）醚（DPEphos）和4,6-双（二苯基膦基）二苯并[b，d]桥接呋喃（DBFphos）。在相应的二金二氯化物与二金二芳基（其中六个是新的）和银（I）盐的配体再分布反应中合成渗析的配合物。渗析的络合物被分离为最小配位阴离子SbF6-和ReO4-的盐。制备四芳基硼酸盐[B（3,5-（CF3）（2）C6H3）（4）]（-）的努力导致了硼的金属转移，同时氟化了芳基配合物结晶。新的配合物的特征在于多核NMR，吸收和发射光谱，77 K发射寿命以及燃烧分析。三个在晶体学上表征。将双双链的芳基配体的结构与单双链的类似物的结构进行比较。晶体结构和密度泛函理论计算均表明，双链金双键会轻微但可观察到芳基配体芳香性的破坏。通过计算检查了一种结构鉴定过的复合物中的分子间亲液相互作用。

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