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New aryloxo allylpalladium complexes

机译:新的芳氧基烯丙基钯配合物

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摘要

Treatment of the di-#mu#-chloride allyl palladium complex [#eta#~3-C_4H_7Pd(#mu#-Cl)_2Pd(#eta#~3-C_4H_7)] with [NBu_4]OH (1:2 molar ratio) in methanol, followed by addition of phenol or para-substituted phenol ArOH (1:2 molar ratio), allows the preparation of dimeric aryloxo complexes of the type [(#eta#~3-C_4H_7)Pd(#mu#-OAr)_2Pd(#eta#~3-C_4H_7)] (Ar=Ph 1, C_6H_4Me-p 2, C_6H_4Cl-p 3, C_6H_4Br-p 4), The addition of p-nitrophenol or pentafluorophenol to complex 1 results in quantitative substitution of the phenoxide anion to give the di-#mu#-aryloxo palladium complexes [(#eta#~3-C_4H_7)Pd(#mu#-OAr)_2Pd(#eta#~3-C_4H_7)] (Ar=C_6H_4NO_2-p 5 or C_6F_5 6). Complexes 1, 5 and 6 react with PPh_3 to give the monomeric aryloxo complexes [(#eta#~3-C_4H_7)Pd(OAr)(PPh_3)] (Ar=Ph 7, C_6H_4NO_2-p 8, C_6F_5 9). The identity of these complexes has been established by partial elemental analyses and NMR (~1H, ~(19)F, ~(13)C and ~(31)P) spectroscopy.
机译:用[NBu_4] OH(摩尔比为1:2)处理二-#mu#-氯化物烯丙基钯配合物[#eta#〜3-C_4H_7Pd(#mu#-Cl)_2Pd(#eta#〜3-C_4H_7)] )在甲醇中,然后加入苯酚或对位取代的苯酚ArOH(摩尔比为1:2),可以制备[[#eta#〜3-C_4H_7)Pd(#mu#-OAr )_2Pd(#eta#〜3-C_4H_7)](Ar = Ph 1,C_6H_4Me-p 2,C_6H_4Cl-p 3,C_6H_4Br-p 4),在配合物1中添加对硝基苯酚或五氟苯酚导致定量取代酚盐阴离子得到二-#mu#-芳基氧基钯络合物[(#eta#〜3-C_4H_7)Pd(#mu#-OAr)_2Pd(#eta#〜3-C_4H_7)](Ar = C_6H_4NO_2-p 5或C_6F_5 6)。配合物1、5和6与PPh_3反应,得到单体芳氧基配合物[(#eta#〜3-C_4H_7)Pd(OAr)(PPh_3)](Ar = Ph 7,C_6H_4NO_2-p 8,C_6F_5 9)。这些配合物的身份已通过部分元素分析和NMR(〜1H,〜(19)F,〜(13)C和〜(31)P)光谱确定。

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