Cyclometalated Iridium Complexes of Bis(Aryl) Phosphine Ligands: Catalytic C–H/C–D Exchanges and C–C Coupling Reactions
作者:Jesús Campos、María F. Espada、Joaquín López-Serrano、Ernesto Carmona
DOI:10.1021/ic400759r
日期:2013.6.3
mode so far encountered only when the phosphine contains two benzylic groups. A base-catalyzed intramolecular, dehydrogenative, C–C coupling reaction converts the κ4 species 5d and 5e into the corresponding hydrido phosphepine complexes 6d and 6e. Using CD3OD as the source of deuterium, the chlorides 2 undergo deuteration of their 11 benzylic positions whereas hydrides 3 experience only D incorporation
这项工作详细说明了合成和一系列的(η的复合物的结构鉴定5 -C 5我5配位环金属化二(芳基)膦配位体)的Ir(III)单元,PR'(Ar)的2,为R'=我和Ar = 2,4,6-箱3 c ^ 6 ħ 2,1B ; 2,6-ME 2 -4-OME-C 6 H ^ 2,1C ; 2,6-ME 2 -4-FC 6 H ^ 2,1D ; R'=的Et中,Ar = 2,6-ME 2 ç 6 ħ 3,1E。分别描述了含氯化物和氢化物的化合物2b - 2e和3b - 3e。氯化物2与NaBAr F(BAr F = B(3,5-C 6 H 3(CF 3)2)4)在CO存在下的反应形成阳离子羰基配合物4 +,且ν(CO)值在窄间隔2030-2040 cm -1,表明这些配合物的Ir(III)中心具有相似的π碱度。在不存在的CO,NaBAr ˚F力κ 4 - P,Ç,Ç ',ç “的金属化臂的协调(研究了所选