17302-37-3Relevant articles and documents
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Glaze,W.H. et al.
, p. 49 - 57 (1972)
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Synthesis of mixed silylene-carbene chelate ligands from nheterocyclic silylcarbenes mediated by nickel
Tan, Gengwen,Enthaler, Stephan,Inoue, Shigeyoshi,Blom, Burgert,Driess, Matthias
supporting information, p. 2214 - 2218 (2015/02/19)
The NiII -mediated tautomerization of the N-heterocyclic hydrosilylcarbene L2Si(H)(CH2)NHC1, where L2 = CH(C=CH2)(CMe)(NAr)2, Ar = 2,6-iPr2C6H3 ; NHC = 3,4,5-trimethylimidazol-2-yliden-6-yl, leads to the first N-heterocyclic silylene (NHSi)-carbene (NHC) chelate ligand in the dibromo nickel(II) complex [L1SiD(CH2)(NHC)NiBr2]2 (L1 = CH(MeC=NAr)2). Reduction of 2 with KC8 in the presence of PMe3 as an auxiliary ligand afforded, depending on the reaction time, the N-heterocyclic silyl-NHC bromo NiII complex [L2Si(CH2)NHCNiBr(PMe3)] 3 and the unique Ni0 complex [h2(Si-H){L2Si(H)(CH2)NHC}Ni(PMe3)2] ,inf>4 featuring an agostic Si-H→!Ni bonding interaction. When 1,2-bis(dimethylphosphino)ethane (DMPE) was employed as an exogenous ligand, the first NHSi-NHC chelate-ligand-stabilized Ni0 complex [L1SiD(CH2)NHCNi(dmpe)] 5 could be isolated. Moreover, the dicarbonyl Ni0 complex 6, [L1SiD-(CH2)NHCNi(CO)2], is easily accessible by the reduction of 2 with K(BHEt3) under a CO atmosphere. The complexes were spectroscopically and structurally characterized. Furthermore, complex 2 can serve as an efficient precatalyst for Kumada-Corriu-type cross-coupling reactions.
The cobalt-catalyzed cross-coupling reaction of alkyl halides with alkyl Grignard reagents: A new route to constructing quaternary carbon centers
Iwasaki, Takanori,Takagawa, Hiroaki,Okamoto, Kanako,Singh, Surya Prakash,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 1583 - 1592 (2014/06/23)
The cross-coupling of alkyl (pseudo)halides with alkyl Grignard reagents is catalyzed efficiently by a cobalt(II) chloride-lithium iodide-1,3-diene catalytic system, which provides a new synthetic tool for constructing sp 3 carbon chains. This system is particularly useful for creating quaternary carbon centers via the use of tertiary alkyl Grignard reagents. Various functional groups including esters, amides and carbamates are well tolerated.