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首页> 外文期刊>Chemistry: A European journal >Chiral Xyliphos Complexes for the Catalytic Imine Hydrogenation Leading to the Metolachlor Herbicide:Isolation of Catlyst-Substrate Adducts
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Chiral Xyliphos Complexes for the Catalytic Imine Hydrogenation Leading to the Metolachlor Herbicide:Isolation of Catlyst-Substrate Adducts

机译：手性木犀草配合物用于催化亚胺加氢生成甲草胺除草剂：催化剂-底物加合物的分离

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Iridium complexes relevant to the catalytic enantioselective hydrogenation of 2-methyl-6-ethylphenyl-1'-methyl-2'-methoxyethylimine (MEA-imine,1)in the Syngenta Metolachlor (3)process were prepared and characterized.Reaction of the diphosphane (S)-1-(R)-2-(diphenylphosphanyl)ferrocenyl]ethyldi(3,5-xylyl)phoshane ((S)-(R)-Xyliphos,(S)-(R)-4)with [Ir_2(mu-Cl)_2(cod)_2](cod=1,5-cyclooctadiene)afforded [Ir(Cl)(cod){(S)-(R)-4}](7),which reacted with AgBF_4 to form [Ir(cod){(S)-(R)-4}]BF_4 (8).Complexes 7 and 8 reacted with iodide to yield [Ir(I)(cod){(S)-(R)-4}](9).When 9 was treated with one and two equivalents of HBF_4,two isomers of the cationic Ir~(III)iodo hydrido complex [Ir(I)(H)(cod){(S)-(R)-4}]BF_4 were isolated (10 and 11,respectively).Complex 9 was oxidized with one equivalent of I_2 to give the iodo-bridged dinuclear species [Ir_2I_2(mu-I)_3{(S)-(R)-4}_2](12).[Ir_2(mu-Cl)_2(coe)_4](13).Complexes 7-12 were structurally characterized by single-crystal X-ray diffraction and tested as single-component catalyst precursors for enantioselective hydrogenation of MEA-imine.Complex 10 and dinuclear complex 12 gave the best catalytic results.Efforts were also directed at isolating substrate-or product-catalyst adducts:Treatment of 8 with 2,6-dimethylphenyl-1'-methyl-2'-methoxyethylimine (DMA-imine,14,a model for 1)under H_2 allowed four isomers of [Ir(H)_2{(S)-(R)-4}(14)]BF_4 (18-21)to be isolmers.These analytically pure isomers were fully characterized by 2D NMR techniques.X-ray structural of an Ir~I-imine adduct,namely,[Ir(C_2H_4)_2(14)]BF_4 (25),which was prepared by reacting [IrCl(C_2H_4)_4]with [Ag(14)_2]BF_4 (16),confirmed the kappa~2 coordination mode of imine 14.
机译：制备并表征了先正甲甲草胺（3）中2-甲基-6-乙基苯基-1'-甲基-2'-甲氧基乙基亚胺（MEA-imine，1）催化对映选择性加氢的铱配合物。 （S）-1-（R）-2-（二苯基膦烷基）二茂铁基]乙基二（3,5-二甲苯基）phoshane（（S）-（R）-木糖，（S）-（R）-4）具有[Ir_2 （mu-Cl）_2（cod）_2]（cod = 1,5-环辛二烯）负载[Ir（Cl）（cod）{（S）-（R）-4}]（7），与AgBF_4反应生成形式[Ir（cod）{（S）-（R）-4}] BF_4（8）。络合物7和8与碘化物反应生成[Ir（I）（cod）{（S）-（R）-4 }]（9）。当9用一当量和两当量的HBF_4处理时，阳离子Ir〜（III）碘代氢化物[Ir（I）（H）（cod）{（S）-（R）的两个异构体-4}] BF_4分离（分别为10和11）。用一当量的I_2氧化络合物9，得到碘桥联的双核物质[Ir_2I_2（mu-I）_3 {（S）-（R）-4 } _2]（12）。[Ir_2（mu-Cl）_2（coe）_4]（13）。通过单晶X射线衍射对复合物7-12进行结构表征和测试络合物10和双核络合物12的催化效果最好，复合物10和双核络合物12的分离效果也很明显.2,6-二甲基苯基- H_2下的1'-甲基-2'-甲氧基乙基亚胺（DMA-亚胺，14，1的模型）允许[Ir（H）_2 {（S）-（R）-4}（14）] BF_4的四个异构体（ 18-21）是异构体。这些分析纯的异构体已通过2D NMR技术进行了充分表征。Ir〜I-亚胺加合物的X射线结构，即[Ir（C_2H_4）_2（14）] BF_4（25），通过使[IrCl（C_2H_4）_4]与[Ag（14）_2] BF_4（16）反应制备，证实了亚胺14的kappa〜2配位模式。

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