Catalysis of Cross-Coupling and Homocoupling Reactions of Aryl Halides Utilizing Ni(0), Ni(I), and Ni(II) Precursors; Ni(0) Compounds as the Probable Catalytic Species but Ni(I) Compounds as Intermediates and Products

Abstract

Both Ni(0) and Ni­(I) compounds are believed to exhibit cross-coupling catalytic properties under various conditions, and the compounds Ni­(PPh3)4 and NiCl­(PPh3)3 are compared as catalysts for representative Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions. The Ni(0) compound exhibits catalytic activities, for cross-coupling of chloro and bromoanisole with phenylboronic acid and of bromobenzene with styrene, yielding results which are comparable with those of many palladium-based catalysts, but our findings with NiCl­(PPh3)3 are at this point unclear. It seems to convert to catalytically active Ni(0) species under Suzuki–Miyaura reaction conditions and is ineffective for Heck–Mizoroki cross-coupling. The paramagnetic Ni­(I) compounds NiX­(PPh3)3 (X = Cl, Br, I) are characterized for the first time by 1H NMR spectroscopy and are found to exhibit broad meta and para resonances at δ 9–11 and 3–4, respectively, and very broad ortho resonances at δ 4−6; these resonances are very useful for detecting Ni­(I) species in solution. The chemical shifts of NiCl­(PPh3)3 vary with the concentration of free PPh3, with which it exchanges, and are also temperature-dependent, consistent with Curie law behavior. The compound trans-NiPhCl­(PPh3)2, the product of oxidative addition of chlorobenzene to Ni­(PPh3)4 and a putative intermediate in cross-coupling reactions of chlorobenzene, is found during the course of this investigation to exhibit entirely unanticipated thermal lability in solution in the absence of free PPh3. It readily decomposes to biphenyl and NiCl­(PPh3)2 in a reaction relevant to the long-known but little-understood nickel-catalyzed conversion of aryl halides to biaryls. Ni­(I) and biphenyl formation is initiated by PPh3 dissociation from trans-NiPhCl­(PPh3)2 and formation of a dinuclear intermediate, a process which is now better defined using DFT methodologies.

Halide Abstraction Competes with Oxidative Addition in the Reactions of Aryl Halides with [Ni(PMenPh(3−n))4]

“…The accessibility of oxidation states +I and +III complicates mechanistic understanding. A number of studies identify Ni I intermediates or products from catalytic reactions, but others suggest that they are often not involved in catalysis . It has been shown that ligand and substrate structure are both crucial in determining the role, if any, of Ni I in catalysis.…”

Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki–Miyaura reactions

“…[9][10][11][12] [Ni(NHC) 2 ] and [Ni(PR 3 ) 4 ] complexes react with aryl halides by oxidative addition or halide abstraction, depending on the ligand and substrate structure. [13][14][15][16][17] [Ni(COD)(dppf)] (1) 18 undergoes oxidative addition to aryl halides, followed by rapid comproportionation to form [NiX(dppf)] ( Fig. 1(a)); 19 we have established the order of reactivity of a series of aryl (pseudo) halides.…”

“…A 'robustness screen' 43,44 was used, in which a model reaction was carried out in the presence of 1 equiv. of each of a series of additives (9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19). ** This provides a rapid and quantitative measure of the effect of each additive.…”

Sulfonated salicylidene thiadiazole complexes with Co (II) and Ni (II) ions as sustainable corrosion inhibitors and catalysts for cross coupling reaction

“…within oxidative addition, (Scheme ). The oxidative addition of Ni‐species has been elucidated by NMR by Manzoor et al . and by Rull et al .…”

“…incorporated new Co (II), Ni (II) and Cu (II) bis ‐(2‐acetylthiophene) oxaloyldihydrazone complexes in Suzuki‐Miyaura reaction of boronic acid with aryl halides in acetonitrile with good impacted catalytic activity of the product yields (from 62% to 82%) . The active catalyst complex as Ni(0) and Ni(I) intermediate compounds in Heck and Suzuki‐Miyaura reaction resulted from one and/or two electron processes in the catalytic cycles, has been detected and studied recently . In particular, air‐stable Ni (II)‐ P^N^P triazine‐phosphine cationic complexes initiated the C―C cross couplings .…”