Improving intramolecular hydroamination Rh(I) and Ir(I) catalysts through targeted ligand modification
Improving intramolecular hydroamination Rh(I) and Ir(I) catalysts through targeted ligand modification
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通过靶向配体修饰改进分子内氢胺化 Rh(I) 和 Ir(I) 催化剂
DOI：
10.1039/b9nj00759h
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发表时间：
2010
影响因子：
3.3
通讯作者：
B. Messerle
中科院分区：
文献类型：
--
作者：
Sophie R. Beeren;S. Dabb;G. Edwards;Matthew K. Smith;A. Willis;B. Messerle
合成了一系列含有膦基吡唑基配体1-(2-(二苯基膦)苯基)吡唑(PyPhP)和1-(2-(二苯基膦)乙基)吡唑(PyP)的配合物：[Ir(PyPhP)(COD)]BPh4、[Ir(PyPhP)(CO)2]BPh4、Rh(PyPhP)(CO)Cl和Ir(PyPhP)(CO)Cl。还使用母体配合物Rh(PyP)(CO)Cl和Rh(PyPhP)(CO)Cl合成了配合物Rh(PyP)(CO)OSO2CF3和Rh(PyPhP)(CO)OSO2CF3。通过X射线衍射分析确定了新配合物的固态结构。阳离子Ir(I)配合物[Ir(PyPhP)(COD)]BPh4被发现是4-戊炔-1-胺分子内氢胺化的高效催化剂，实现了1500 h−1的周转率，6分钟内转化率>98%。通过与 AgOSO2CF3、TMSOSO2CF3 或 NaBPh4 反应提取氯配体，原位生成活性催化剂，显着提高了使用中性 Ir(I) 和 Rh(I) 配合物作为催化剂的 4-戊炔-1-胺催化氢胺化的效率。发现由 Ir(PyP)(CO)Cl 和钠盐生成的催化剂的催化效率与钠盐抗衡离子的配位强度成反比。 Rh(PyP)(CO)OSO2CF3 是一种比 AgOSO2CF3 和氯化物配合物 Rh(PyP)(CO)Cl 原位生成的配合物更有效的 4-戊炔-1-胺环化催化剂，表明与 Rh(PyP)(CO)Cl 的氯化物配合物相比，Rh(PyP)(CO)OSO2CF3 的三氟甲磺酸酯配合物具有更高的不稳定性，增强了Rh(I)配合物的催化活性。
A series of complexes containing the phosphino-pyrazolyl ligand 1-(2-(diphenylphosphino)phenyl)pyrazole (PyPhP) and 1-(2-(diphenylphosphino)ethyl)pyrazole (PyP) were synthesized: [Ir(PyPhP)(COD)]BPh4, [Ir(PyPhP)(CO)2]BPh4, Rh(PyPhP)(CO)Cl and Ir(PyPhP)(CO)Cl. The complexes Rh(PyP)(CO)OSO2CF3 and Rh(PyPhP)(CO)OSO2CF3 were also synthesized, using the parent complexes Rh(PyP)(CO)Cl and Rh(PyPhP)(CO)Cl. The solid-state structures of the new complexes were determined by X-ray diffraction analysis. The cationic Ir(I) complex [Ir(PyPhP)(COD)]BPh4 was found to be a highly efficient catalyst for the intramolecular hydroamination of 4-pentyn-1-amine, achieving a turnover rate of 1500 h−1, with >98% conversion in 6 minutes. The efficiency of the catalyzed hydroamination of 4-pentyn-1-amine using the neutral Ir(I) and Rh(I) complexes as catalysts was significantly improved by generating active catalysts in situ through abstraction of a chloride ligand by reaction with AgOSO2CF3, TMSOSO2CF3 or NaBPh4. The catalytic efficiency of the catalysts generated from Ir(PyP)(CO)Cl and a sodium salt were found to be inversely proportional to the coordinating strength of the counter-ion of the sodium salt. Rh(PyP)(CO)OSO2CF3 is a more efficient catalyst for the cyclization of 4-pentyn-1-amine than the complex generated in situ from AgOSO2CF3 and chloride complex Rh(PyP)(CO)Cl indicating that the higher lability of the triflate co-ligand of Rh(PyP)(CO)OSO2CF3, compared to the chloride co-ligand of Rh(PyP)(CO)Cl, enhances the catalytic activity of the Rh(I) complexes.
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影响因子：
5.2
作者：
Schlummer, B;Hartwig, JF
通讯作者：
Hartwig, JF
影响因子：
15
作者：
Utsunomiya, M;Hartwig, JF
通讯作者：
Hartwig, JF
影响因子：
15
作者：
L. Ackermann;R. Bergman;Rebecca N. Loy
通讯作者：
L. Ackermann;R. Bergman;Rebecca N. Loy
影响因子：
15
作者：
Anderson, LL;Arnold, J;Bergman, RG
通讯作者：
Bergman, RG
影响因子：
15
作者：
Liu, Zhijian;Hartwig, John F.
通讯作者：
Hartwig, John F.