74910-03-5Relevant articles and documents
Intermediacy of Ni-Ni Species in sp2 C-O Bond Cleavage of Aryl Esters: Relevance in Catalytic C-Si Bond Formation
Somerville, Rosie J.,Hale, Lillian V. A.,Gómez-Bengoa, Enrique,Burés, Jordi,Martin, Ruben
, p. 8771 - 8780 (2018)
Monodentate phosphine ligands are frequently employed in the Ni-catalyzed C-O functionalization of aryl esters. However, the extensive body of preparative work on such reactions contrasts with the lack of information concerning the structure and reactivity of the relevant nickel intermediates. In fact, experimental evidence for a seemingly trivial oxidative addition into the C-O bond of aryl esters with monodentate phosphines and low-valent nickel complexes still remains elusive. Herein, we report a combined experimental and theoretical study on the Ni(0)/PCy3-catalyzed silylation of aryl pivalates with CuF2/CsF additives that reveals the involvement of unorthodox dinickel oxidative addition complexes in C-O bond cleavage and their relevance in C-Si bond formation. We have obtained a mechanistic picture that clarifies the role of the additives and demonstrates that dinickel complexes act as reservoirs of the propagating monomeric nickel complexes by disproportionation. We believe this study will serve as a useful entry point to unravelling the mechanistic underpinnings of other related Ni-catalyzed C-O functionalization reactions employing monodentate phosphines.
REAKTIONEN VON HETEROOLEFINEN AN ZENTRALMETALLEN IN NIEDRIGEN OXIDATIONSSTUFEN: STABILE ALDEHYDKOMPLEXE DES NICKEL(0) UND VERWANDTE VERBINDUNGEN
Walther, Dirk
, p. 393 - 402 (2007/10/02)
Nickel(0) complex moieties with a high electron density at the central atom are able to yield stable complexes with many aromatic aldehydes. 1H NMR spectroscopic data give evidence about olefin-like bonding of the aldehyde group and indicate a high charge transfer.Chelate ligands like tetramethylethylenediamine yield stable complexes of the composition (TME)NiL (L = aldehyde, benzil, α,β-unsaturated carbonyl compounds).Some reactions and properties of typical mixed ligand complexes are described.
