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Effects of Additives on Catalytic Arene C–H Activation: Study of Rh Catalysts Supported by Bis-phosphine Pincer Ligands
Organometallics ( IF 2.5 ) Pub Date : 2020-10-29 , DOI: 10.1021/acs.organomet.0c00623 Fanji Kong 1 , Shunyan Gu 1 , Chang Liu 1 , Diane A. Dickie 1 , Sen Zhang 1 , T. Brent Gunnoe 1
Organometallics ( IF 2.5 ) Pub Date : 2020-10-29 , DOI: 10.1021/acs.organomet.0c00623 Fanji Kong 1 , Shunyan Gu 1 , Chang Liu 1 , Diane A. Dickie 1 , Sen Zhang 1 , T. Brent Gunnoe 1
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Hydrogen–deuterium exchange (H/D exchange) is a method commonly used for studying catalytic activation of C–H(D) bonds by transition metal complexes. In this study, a series of additives were studied for H/D exchange of toluene-d8 with acetic acid (HOAc) using (RPNP)Rh(X) complexes (R = phosphine substituents including cyclohexyl, isopropyl, and tert-butyl; X = trifluoroacetate or acetate) as the precatalysts. Cu(OAc)2 and AgOAc additives were found to benefit Rh-mediated C–H(D) activation of toluene with meta–para selectivity by facilitating the conversion to active (RPNP)Rh species and stabilizing the Rh catalysts from decomposition to inactive Rh(s). In contrast, nonoxidizing Lewis acid additives, such as B(OMe)3 or NaOAc, were not effective at facilitating Rh-catalyzed toluene C–H activation. The complexes (RPNP)RhIII(H)(X)2 and [(RPNP)RhI(CO)][X] (X = TFA or OAc) were found to be intermediates of the catalytic the H/D exchange.
中文翻译：
添加剂对芳烃CH–H活化的影响：双膦钳型配体负载的Rh催化剂的研究
氢-氘交换（H / D交换）是一种通常用于研究过渡金属配合物催化C-H（D）键的催化活化的方法。在这项研究中，一系列的添加剂进行了研究为甲苯的H / d交换d 8，使用（用乙酸（HOAc）纯化ř PNP）的Rh（X）配合物（R =膦取代基，包括环己基，异丙基和叔丁基； X ＝三氟乙酸盐或乙酸盐）作为前催化剂。发现Cu（OAc）2和AgOAc添加剂通过促进向活性物质（R的转化）有利于Rh介导的甲苯对C–H（D）活化和间-对选择性的活化。PNP）Rh物种，并稳定Rh催化剂从分解到失活的Rh。相反，非氧化路易斯酸添加剂，例如B（OMe）3或NaOAc，在促进Rh催化的甲苯CH活化方面无效。发现络合物（R PNP）Rh III（H）（X）2和[（R PNP）Rh I（CO）] [X]（X = TFA或OAc）是催化H / D交换的中间体。
更新日期：2020-11-09
中文翻译：
添加剂对芳烃CH–H活化的影响：双膦钳型配体负载的Rh催化剂的研究
氢-氘交换（H / D交换）是一种通常用于研究过渡金属配合物催化C-H（D）键的催化活化的方法。在这项研究中，一系列的添加剂进行了研究为甲苯的H / d交换d 8，使用（用乙酸（HOAc）纯化ř PNP）的Rh（X）配合物（R =膦取代基，包括环己基，异丙基和叔丁基； X ＝三氟乙酸盐或乙酸盐）作为前催化剂。发现Cu（OAc）2和AgOAc添加剂通过促进向活性物质（R的转化）有利于Rh介导的甲苯对C–H（D）活化和间-对选择性的活化。PNP）Rh物种，并稳定Rh催化剂从分解到失活的Rh。相反，非氧化路易斯酸添加剂，例如B（OMe）3或NaOAc，在促进Rh催化的甲苯CH活化方面无效。发现络合物（R PNP）Rh III（H）（X）2和[（R PNP）Rh I（CO）] [X]（X = TFA或OAc）是催化H / D交换的中间体。
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