CH 3 –X Reductive Elimination Reactivity of Pt IV Me Complexes Supported by a Sulfonated CNN Pincer Ligand (X = OH, CF 3 CO 2 , PhNMe 2 + )
CH 3 –X Reductive Elimination Reactivity of Pt IV Me Complexes Supported by a Sulfonated CNN Pincer Ligand (X = OH, CF 3 CO 2 , PhNMe 2 + )
复制标题
磺化 CNN Pincer 配体支持的 Pt IV Me 配合物的 CH 3 →X 还原消除反应性 (X = OH, CF 3 CO 2 , PhNMe 2 )
DOI：
10.1021/acs.organomet.9b00702
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发表时间：
2019
期刊：
影响因子：
2.8
通讯作者：
Vedernikov, Andrei N.
中科院分区：
文献类型：
--
作者：
Ruan, Jiaheng;Wang, Daoyong;Vedernikov, Andrei N.
合成并表征了三个新的磺化CNN钳形配体L固载的二烃基LPtIVMe(Y)配合物(6-8；Y=Cl，I，OCH2CF3)。研究了这些配合物在2，2，2-三氟乙醇(TFE)和二甲基亚砜(DMSO)中与多种亲核试剂(H2O、CF3CO2-、Me2SO、PhNMe2)反应生成相应的C-X偶联产物CH3-X的反应。在22℃的TFE或DMSO溶液中，在PhNMe2的存在下，观察到6-8个C-N偶联产物PhNMe3+的定量生成，反应活性按6>；7>；8的顺序递减。在TFE溶液中使用NaO_2CCF_3效率较低，导致在70℃下22 h后MeO_2CCF_3的产率为60%，在DMSO中，当三氟乙酸水溶液在80℃下反应3 h后，C-O偶联反应的产率为87%，或者当NaO_2CCF_3在80℃下反应1.5h后生成MeO_2CCF_3时，产率为80%，MeSO+是次要的副产物。6-8与PhNMe2在TFE中反应的动力学研究揭示了总的二级速率规律d[PhNMe3+]/dt=K2[6，7或8][PhNMe2]，与SN2型过程的实现一致。对TFE中7和PhNMe2之间的几种替代反应路径的密度泛函模拟支持了PhNMe2在7的甲基碳上的直接亲核攻击是这种转化的最可能的机制。
Three new dihydrocarbyl LPtIVMe(Y) complexes (6–8; Y = Cl, I, OCH2CF3) supported by the sulfonated CNN pincer ligand L have been prepared and characterized. The reaction of these complexes with a number of nucleophiles (H2O, CF3CO2–, Me2SO, PhNMe2) resulting in the formation of corresponding C–X coupled products CH3–X has been studied in 2,2,2-trifluoroethanol (TFE) and DMSO. In TFE or DMSO solutions at 22 °C, in the presence of PhNMe2, a quantitative formation of a C–N coupled product, PhNMe3+, was observed for6–8, with the reactivity decreasing in the order6>7>8. The use of NaO2CCF3in TFE solutions was less efficient, leading to the production of MeO2CCF3in 60% yield after 22 h at 70 °C. In DMSO the C–O coupling was high yielding when aqueous trifluoroacetic acid was used to produce methanol (87% after 3 h at 80 °C) or when NaO2CCF3was used to form MeO2CCF3(80% after 1.5 h at 80 °C), with Me3SO+being a minor byproduct. The kinetics study of the reaction between6–8and PhNMe2in TFE has revealed an overall second-order rate law, d[PhNMe3+]/dt=k2[6,7or8][PhNMe2], consistent with the realization of an SN2-type process. A DFT modeling of several alternative pathways of reaction between7and PhNMe2in TFE supported the direct nucleophilic attack of PhNMe2at the methyl group carbon of7as the most likely mechanism of this transformation.