In situ transformations of Pd/NHC complexes with N-heterocyclic carbene ligands of different nature into colloidal Pd nanoparticles

被引:22
|
作者
Kostyukovich, Alexander Yu. [1 ]
Tsedilin, Andrey M. [1 ]
Sushchenko, Ekaterina D. [1 ]
Eremin, Dmitry B. [1 ]
Kashin, Alexey S. [1 ]
Topchiy, Maxim A. [2 ,3 ]
Asachenko, Andrey F. [2 ,3 ]
Nechaev, Mikhail S. [2 ,3 ]
Ananikov, Valentine P. [1 ,2 ]
机构
[1] Russian Acad Sci, Zelinsky Inst Organ Chem, Leninsky Pr 47, Moscow 119991, Russia
[2] Moscow MV Lomonosov State Univ, Leninskie Gory 1 3, Moscow 119991, Russia
[3] Russian Acad Sci, AV Topchiev Inst Petrochem Synth, Leninsky Prospect 29, Moscow 119991, Russia
来源
INORGANIC CHEMISTRY FRONTIERS | 2019年 / 6卷 / 02期
基金
俄罗斯科学基金会;
关键词
DENSITY-FUNCTIONAL THEORY; HETEROATOM BOND FORMATION; REDUCTIVE ELIMINATION; OXIDATIVE ADDITION; PALLADIUM COMPLEXES; C-C; NICKEL; NHC; CHEMISTRY; CATALYSTS;
D O I
10.1039/c8qi01095a
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
R-NHC coupling was previously considered as a process of degradation of M/NHC species; however recent studies have pointed out that it may be responsible for the generation of catalytically active NHC-free complexes and/or metallic nanoparticles. Therefore, a detailed and systematic study of R-NHC coupling for various carbene ligands is an important topic. In the present article this process has been studied for reactive aryl iodide coupling partners by a combination of quantum chemical calculations and continuous reaction monitoring via pressurized sample infusion electrospray ionization mass spectrometry (PSI-ESI-MS). DFT calculations revealed a strong tendency of (NHC)Pd(Ph)(I)DMF complexes bearing various N-heterocyclic carbene (NHC) ligands to undergo Ph-NHC coupling. Calculated energy barriers of these reactions lie in the range of 17.9-25.1 kcal mol(-1). Ph-NHC coupling is thermodynamically more favorable for the complexes containing unsaturated NHC ligands with bulky substituents. NBO analysis suggests that the process of Ph-NHC formation is similar for different NHC ligands. In order to confirm the results of theoretical studies, a series of ESI-MS reaction monitoring experiments were performed for (NHC)Pd(i)(2)(Py) and (NHC)Pd(Cl)((3)-1-Ph-C3H4) complexes interacting with iodobenzene, where Ph-NHC coupling products were observed in all cases. As direct experimental evidence, the formation of colloidal Pd-containing nanoparticles was observed in situ for different Pd/NHC complexes in the studied reaction mixtures.
引用
收藏
页码:482 / 492
页数:11
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