Catalytic C-F Bond Hydrogenolysis of Fluoroaromatics by [(η5‑C5Me5)RhI(2,2′-bipyridine)]

Catalytic C-F Bond Hydrogenolysis of Fluoroaromatics by [(η5‑C5Me5)RhI(2,2′-bipyridine)]
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[(η5-C5Me5)RhI(2,2′-联吡啶)]催化氟代芳烃C-F键氢解

DOI:
10.1021/om500647h
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发表时间:
2014
期刊:
影响因子:
2.8
通讯作者:
Seiji
Seiji
中科院分区:
化学2区
文献类型:
--
作者:
Nakai;Hidetaka; Jeong;Kihun; Matsumoto;Takahiro; Ogo;Seiji

文献摘要

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本文报道了一种新型的含氟芳烃(C_6F_5CF_3,C_6F_6,C_6F_5H和C_6F_5CH_3)C-F键氢解反应的高效催化剂--Rh(I)配合物[(η_5-C_5Me_5)RhI(bpy)](1; bpy = 2,2 ′-联吡啶)。C6 F6的最佳转化数为380,通过使用0.1 mol %的1、0.8 MPa的H2和2当量的Et 2NH在CH 3CN中在25 °C下获得。成功地分离出C-F键断裂产物[(η5-C5 Me 5)RhIII(bpy)(C6 F5)](F)作为C6 F6 by 1催化氢解的可能中间体。
A new class of efficient catalyst, the Rh(I) complex [(η5-C5Me5)RhI(bpy)] (1; bpy = 2,2′-bipyridine), for the C–F bond hydrogenolysis of fluoroaromatics (C6F5CF3, C6F6, C6F5H, and C6F5CH3) is presented. The best turnover number of 380 for C6F6is afforded by using 0.1 mol % of1, 0.8 MPa of H2, and 2 equiv of Et2NH in CH3CN at 25 °C. The successful isolation of the C–F bond cleavage product [(η5-C5Me5)RhIII(bpy)(C6F5)](F) as a plausible intermediate of the catalytic hydrogenolysis of C6F6by1is also described.