雷那苯并嗪配合物的合成与表征。

Synthesis and characterization of rhenabenzyne complexes.

机构信息

Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.

出版信息

Chemistry. 2012 Oct 29;18(44):14128-39. doi: 10.1002/chem.201202012. Epub 2012 Sep 17.

DOI:10.1002/chem.201202012

Abstract

Reactions of [ReH(5)(PMe(2)Ph)(3)] with alkynols HC≡CC(OH)(R)C≡CSiMe(3) (R=tBu, iPr, 1-adamantyl) in the presence of HCl give the vinylcarbyne complexes [Re{≡CCH=C(R)C≡CSiMe(3)}Cl(2)(PMe(2)Ph)(3)], which react with tBuMgCl to give [Re{≡CCH=C(R)C≡CSiMe(3)}HCl(PMe(2)Ph)(3)]. Treatment of [Re{≡CCH=C(R)C≡CSiMe(3)}HCl(PMe(2)Ph)(3)] with nBu(4)NF gives [Re{≡CCH=C(R)C≡CH}HCl(PMe(2)Ph)(3)], which first isomerizes to the bicyclic complexes [Re{CH=CH-C(R)=CCH=}Cl(PMe(2)Ph)(3)], and then to the rhenabenzynes [Re{≡CCH=C(R)CH=CH}Cl(PMe(2)Ph)(3)]. The NMR spectroscopic and structural data as well as the aromatic stabilization energy (ASE) and nucleus-independent chemical-shift (NICS) values suggest that these rhenabenzynes have aromatic character.

摘要

在 HCl 的存在下，[ReH(5)(PMe(2)Ph)(3)]与炔醇 HC≡CC(OH)(R)C≡CSiMe(3)（R=tBu，iPr，1-金刚烷基）反应生成乙烯基卡宾配合物[Re{≡CCH=C(R)C≡CSiMe(3)}Cl(2)(PMe(2)Ph)(3)]，其与 tBuMgCl 反应生成[Re{≡CCH=C(R)C≡CSiMe(3)}HCl(PMe(2)Ph)(3)]。用 nBu(4)NF 处理[Re{≡CCH=C(R)C≡CSiMe(3)}HCl(PMe(2)Ph)(3)]得到[Re{≡CCH=C(R)C≡CH}HCl(PMe(2)Ph)(3)]，其首先异构化为双环配合物[Re{CH=CH-C(R)=CCH=}Cl(PMe(2)Ph)(3)]，然后转化为铼苯炔[Re{≡CCH=C(R)CH=CH}Cl(PMe(2)Ph)(3)]。核磁共振谱和结构数据以及芳香稳定能（ASE）和核独立化学位移（NICS）值表明，这些铼苯炔具有芳香性。