作者:Hiro-omi Taguchi、Yung-Hung Chang、Katsuhiko Takeuchi、Fumiyuki Ozawa
DOI:10.1021/acs.organomet.5b00195
日期:2015.4.27
An unsymmetrical PNP-pincer-type phosphaalkene ligand, 2-(phospholanylmethyl)-6-(2-phosphaethenyl)pyridine (PPEP), has been prepared from 2,6-bis(2-phosphaethenyl)pyridine (BPEP) by intramolecular C–H addition/cyclization of the 2-phosphaethenyl group with a 2,4,6-tri-tert-butylphenyl substituent (CH═PMes*). The reaction proceeds in hexane in the presence of a catalytic amount of [Pt(PCy3)2] (20 mol
一种不对称的PNP钳型磷烯烃配体2-(磷戊基甲基)-6-(2-磷乙烯基)吡啶(PPEP)是由2,6-双(2-磷乙烯基)吡啶(BPEP)通过分子内C– 2- phosphaethenyl基团的H加法/环化与2,4,6-三-叔丁基苯基的取代基(CH═PMes*)。反应在己烷中,在密封管中于80°C,催化量[Pt(PCy 3)2 ](20摩尔%)存在下进行,得到PPEP,分离产率为32%,同时副产物2,6 -双(磷杂环戊烷基甲基)吡啶(BPMP)和Pt(II)膦酰氨基复合物(5)。PPEP配体与[Rh(μ-Cl)(C 2 H 4)2 ] 2和[RuCl2(PPh 3)3 ]分别得到[RhCl(PPEP)](6)和[RuCl 2(PPh 3)(PPEP)](8)。配合物6容易在其他CH═PMes*基团上进行C–H加成/环化反应,得到2,6-双(磷杂环戊烷基甲基)吡啶配合物[RhCl(BPMP)](7),而8对C–H加成稳定。