Fate of Aryl/Amido Complexes of Rhodium(III) Supported by a POCOP Pincer Ligand: C–N Reductive Elimination, β-Hydrogen Elimination, and Relevance to Catalysis
Fate of Aryl/Amido Complexes of Rhodium(III) Supported by a POCOP Pincer Ligand: C–N Reductive Elimination, β-Hydrogen Elimination, and Relevance to Catalysis
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POCOP 钳形配体支持的铑 (III) 芳基/氨基配合物的命运：C-N 还原消除、β-氢消除以及与催化的相关性
DOI：
10.1021/om500577w
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发表时间：
2014
期刊：
影响因子：
2.8
通讯作者：
O. Ozerov
中科院分区：
文献类型：
--
作者：
Samuel D. Timpa;Christopher J. Pell;Jia Zhou;O. Ozerov
铑配合物由芳基/双（亚膦酸盐）POCOP钳形配体支撑，形成了类似于经典Pd0/PdII Buchwald-Hartwig化学的RhI/RhIII合成循环。（POCOP）Rh(H)(Cl)(1)和NaOtBu原位生成的（POCOP）Rh片段，通过将ArX氧化加入（POCOP）Rh(Ar)(X)配合物（X = Cl, Br），可以很容易地得到（POCOP）Rh(Ar)(X)配合物。（POCOP）Rh(Ar)(X)配合物在等摩尔量的NaOtBu存在下与苯胺和二苯胺反应生成RhIII芳基/胺配合物（POCOP）Rh(Ar)（NHAr '）和（POCOP）Rh(Ar)（NPh2）。中间产物（POCOP）Rh(p-F3CC6H4)(OtBu)(7)与p-MeC6H4NH2发生不可逆反应生成（POCOP）Rh(p-F3CC6H4)(NHC6H4Me-p)(5)。后者加热后还原消除二芳胺产物p-F3CC6H4NHC6H4Me-p。该反应的动力学指向一级过程，DFT计算确定了协同C-N还原消除的过渡态。复合体1号生效…
Rhodium complexes supported by the aryl/bis(phosphinite) POCOP pincer ligand undergo reactions that constitute a RhI/RhIII synthetic cycle for C–N coupling analogous to the classical Pd0/PdII Buchwald–Hartwig chemistry. (POCOP)Rh(Ar)(X) complexes (X = Cl, Br) can be readily obtained by oxidative addition of ArX to the (POCOP)Rh fragment generated in situ from (POCOP)Rh(H)(Cl) (1) and NaOtBu. (POCOP)Rh(Ar)(X) complexes react with anilines and diphenylamine in the presence of an equimolar amount of NaOtBu to give RhIII aryl/amido complexes (POCOP)Rh(Ar)(NHAr′) and (POCOP)Rh(Ar)(NPh2). The intermediate (POCOP)Rh(p-F3CC6H4)(OtBu) (7) was isolated and shown to react irreversibly with p-MeC6H4NH2 to give (POCOP)Rh(p-F3CC6H4)(NHC6H4Me-p) (5). The latter undergoes reductive elimination of the diarylamine product p-F3CC6H4NHC6H4Me-p upon heating. The kinetics of this reaction point to a first-order process, and DFT calculations located a transition state for concerted C–N reductive elimination. Complex 1 effected ...
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影响因子：
8.4
作者：
Maiti D;Fors BP;Henderson JL;Nakamura Y;Buchwald SL
通讯作者：
Buchwald SL
影响因子：
15
作者：
Fors BP;Davis NR;Buchwald SL
通讯作者：
Buchwald SL
影响因子：
15
作者：
Shen, Qilong;Ogata, Tokutaro;Hartwig, John F.
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Hartwig, John F.
影响因子：
8.4
作者：
Bruno NC;Tudge MT;Buchwald SL
通讯作者：
Buchwald SL
影响因子：
15
作者：
Fors, Brett P.;Watson, Donald A.;Biscoe, Mark R.;Buchwald, Stephen L.
通讯作者：
Buchwald, Stephen L.