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Iridium and rhodium “PNP” aminodiphosphine complexes used as catalysts in the oxidation of styrene

机译:铱和铑“PNP”氨基膦络合物用作苯乙烯氧化中的催化剂

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Six PNP or aminodiphosphine ligands were synthesized and complexed to the transition metals iridium and rhodium to give [(η ~(5) -C _(5) Me _(5) )MCl{η ~(2) - P , P ′-(PPh _(2) ) _(2) NR}]PF _(6) , where M = Ir ( 1 ) and Rh ( 2 ) and R = cyclohexyl ( a ), iso-propyl ( b ), pentyl ( c ), phenyl ( d ), chlorophenyl ( e ) and methoxyphenyl ( f ). These complexes were fully characterized by NMR, elemental analyses and IR spectroscopy. Crystals of 1f and 2f were obtained, which showed a distorted octahedral geometry around the metal centers. These complexes showed good activity in the oxidation of styrene using tert -butyl hydroperoxide (TBHP) as the oxidant. The iridium complexes were more active than the rhodium complexes. Higher yields for benzaldehyde were achieved in comparison to styrene oxide for all catalysts.
机译:合成六种PNP或氨基双膦配体,并络合到过渡金属铱和铑,得到[(η〜(5)-C _(5)Me _(5))Mcl {η〜(2) - p,p' - (PPH _(2))_(2)NR}] PF _(6),其中M = IR(1)和RH(2)和R =环己基(A),异丙基(B),戊基(C ),苯基(D),氯苯基(E)和甲氧基苯基(F)。这些配合物通过NMR,元素分析和IR光谱完全表征。获得了1F和2F的晶体,其在金属中心周围显示出扭曲的八面体几何形状。这些配合物在使用叔丁基氢过氧化物(TBHP)作为氧化剂的苯乙烯氧化良好的活性。铱络合物比铑配合物更活跃。与所有催化剂的苯乙烯氧化物相比,实现了苯甲醛的更高产率。

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