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81.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(51):16585-16588
Readily accessed cobalt pre‐catalysts with N‐heterocyclic carbene ligands catalyze the Suzuki cross‐coupling of aryl chlorides and bromides with alkyllithium‐activated arylboronic pinacolate esters. Preliminary mechanistic studies indicate that the cobalt species is reduced to Co0 during the reaction. 相似文献
82.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(26):7681-7686
The trapping of a silicon(I) radical with N‐heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6‐i Pr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I− ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAACMe−H]+I−. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I− ( 2 ) comprising the first NHC–parent‐silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr−H bond activation product [1‐F‐2‐IMe‐C6H4]+I− ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X‐ray crystallography. 相似文献
83.
Xiaoyu Ren Dr. Christophe Gourlaouen Dr. Marcel Wesolek Dr. Pierre Braunstein 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(41):12731-12734
The imidazolium chloride [C3H3N(C3H6NMe2)N{C(Me)(=NDipp)}]Cl ( 1 ; Dipp=2,6‐diisopropyl phenyl), a potential precursor to a tritopic NimineCNHCNamine pincer‐type ligand, reacted with [Ni(cod)2] to give the NiI‐NiI complex 2 , which contains a rare cod‐derived η3‐allyl‐type bridging ligand. The implied intermediate formation of a nickel hydride through oxidative addition of the imidazolium C−H bond did not occur with the symmetrical imidazolium chloride [C3H3N2{C(Me)(=NDipp)}2]Cl ( 3 ). Instead, a Ni−C(sp3) bond was formed, leading to the neutral NimineCHNimine pincer‐type complex Ni[C3H3N2{C(Me)(=NDipp)}2]Cl ( 4 ). Theoretical studies showed that this highly unusual feature in nickel NHC chemistry is due to steric constraints induced by the N substituents, which prevent Ni−H bond formation. Remarkably, ethylene inserted into the C(sp3)−H bond of 4 without nickel hydride formation, thus suggesting new pathways for the alkylation of non‐activated C−H bonds. 相似文献
84.
The novel catalytic system, composed of a ruthenium alkylidene containing a surfactant fragment in the catalysts molecule, is reported. Ring closing metathesis and cross metathesis reactions proceed efficiently in neat water at room temperature, in air, without need of adding an external surfactant. 相似文献
85.
86.
A new C2-symmetric chelating di-N-heterocyclic carbene (NHC) ligand is reported. The stable free di-carbene (+/−)[DEAM-BY] (3) forms upon treating the imidazolium salt (+/−)[DEAM-BI][OTf]2 (2) with potassium bis-trimethylsilylamide (where DEAM-BY = trans-9,10-dihydro-9,10-ethanoanthracene-11,12-bis(1-benzyl)imidaz-2-ylidene and DEAM-BI = trans-9,10-dihydro-9,10-ethanoanthracene-11,12-bis(1-benzyl)imidazolium). Metalation reactions of 2 with [Rh(COD)Cl]2 and [Ir(COD)Cl]2 are carried out under mild conditions to produce either mono- or bimetallic complexes. Each compound is characterized by NMR spectroscopy, combustion analysis, and single-crystal X-ray crystallography. 相似文献
87.
The synthesis of two N-aryl substituted 2-silaimidazolidenes 9a, b by metal-reduction of the appropriate silicon(IV) heterocycles is reported. Structural as well as spectroscopic data obtained for the N-aryl substituted N-heterocyclic silylenes (NHSi) are very close to those obtained previously for their N-alkyl substituted counterparts. NHSis 9a, b are used as starting materials for the synthesis of a series of dichalcogenadisiletanes 19-24 and for of a mono silylene tungsten complex 29. The reactivity studies revealed only marginally differences between the N-aryl substituted NHSis 9a, b and previously described N-alkyl substituted silylenes. 相似文献
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