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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.
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页码:482 / 492
页数:11
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