74945-90-7Relevant academic research and scientific papers
Mechanistic study of an improved Ni precatalyst for Suzuki-Miyaura reactions of aryl sulfamates: Understanding the role of Ni(I) species
Beromi, Megan Mohadjer,Nova, Ainara,Balcells, David,Brasacchio, Ann M.,Brudvig, Gary W.,Guard, Louise M.,Hazari, Nilay,Vinyard, David J.
supporting information, p. 922 - 936 (2017/05/16)
Nickel precatalysts are potentially a more sustainable alternative to traditional palladium precatalysts for the Suzuki-Miyaura coupling reaction. Currently, there is significant interest in Suzuki-Miyaura coupling reactions involving readily accessible phenolic derivatives such as aryl sulfamates, as the sulfamate moiety can act as a directing group for the prefunctionalization of the aromatic backbone of the electrophile prior to cross-coupling. By evaluating complexes in the Ni(0), (I), and (II) oxidation states we report a precatalyst, (dppf)Ni(σ-tolyl)(Cl) (dppf = 1,1'-bis(diphenylphosphino)-ferrocene), for Suzuki-Miyaura coupling reactions involving aryl sulfamates and boronic acids, which operates at a significantly lower catalyst loading and at milder reaction conditions than other reported systems. In some cases it can even function at room temperature. Mechanistic studies on precatalyst activation and the speciation of nickel during catalysis reveal that Ni(I) species are formed in the catalytic reaction via two different pathways: (i) the precatalyst (dppf)Ni(σ-tolyl)(Cl) undergoes comproportionation with the active Ni(0) species; and (ii) the catalytic intermediate (dppf)Ni(Ar) (sulfamate) (Ar = aryl) undergoes comproportionation with the active Ni(0) species. In both cases the formation of Ni(I) is detrimental to catalysis, which is proposed to proceed via a Ni(0)/Ni(II) cycle. DFT calculations are used to support experimental observations and provide insight about the elementary steps involved in reactions directly on the catalytic cycle, as well as off-cycle processes. Our mechanistic investigation provides guidelines for designing even more active nickel catalysts.
TRANSITION METAL ALLYLS IV. THE (η3-ALLYL)2M COMPLEXES OF NICKEL, PALLADIUM AND PLATINUM: REACTION WITH TERTIARY PHOSPHINES
Henc, B.,Jolly, P.W.,Salz, R.,Stobbe, S.,Wilke, G.,et al.
, p. 449 - 476 (2007/10/02)
A series of 1:1 adducts have been prepared by treating the bis-η3-allyl complexes of nickel, palladium and platinum with tertiary phosphines.Investigations of their structure in solution as well as in the crystal have shown that both 18-electron (η3-allyl)2M-L complexes as well as 16-electron (η1-allyl)-(η3-allyl)M-L complexes may be formed.
