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Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0).

ABSTRACT: Current methods for Suzuki-Miyaura couplings of nontriflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe₃, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the presence of aryl chlorides. This selectivity was exploited in the first Ni-catalyzed C-O-selective Suzuki-Miyaura coupling of chlorinated phenol derivatives where the oxygen-containing leaving group is not a fluorinated sulfonate such as triflate. Computational studies suggest that the origin of divergent selectivity between PMe₃ and other phosphines differs from prior examples of ligand-controlled chemodivergent cross-couplings. PMe₃ effects selective reaction at tosylate due to both electronic and steric factors. A close interaction between nickel and a sulfonyl oxygen of tosylate during oxidative addition is critical to the observed selectivity.

SUBMITTER: Entz ED

PROVIDER: S-EPMC8082739 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0).

Entz Emily D ED Russell John E A JEA Hooker Leidy V LV Neufeldt Sharon R SR

Journal of the American Chemical Society 20200828 36

Current methods for Suzuki-Miyaura couplings of nontriflate phenol derivatives are limited by their intolerance of halides including aryl chlorides. This is because Ni(0) and Pd(0) often undergo oxidative addition of organohalides at a similar or faster rate than most Ar-O bonds. DFT and stoichiometric oxidative addition studies demonstrate that small phosphines, in particular PMe<sub>3</sub>, are unique in promoting preferential reaction of Ni(0) with aryl tosylates and other C-O bonds in the p ...[more]

PMID: 32805116

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Project description:The syntheses of three series of complexes designed with self-complementary motifs for formation of halogen bonds between an iodotetrafluorophenyl ligand and a halide ligand at square-planar nickel are reported, allowing structural comparisons of halogen bonding between all four halides C6F4I···X-Ni (X = F, Cl, Br, I). In the series trans-[NiX(2,3,5,6-C6F4I)(PEt3)2] 1pX and trans-[NiX(2,3,4,5-C6F4I)(PEt3)2] (X = F, Cl, Br, I) 1oX, the iodine substituent on the benzene ring was positioned para and ortho to the metal, respectively. The phosphine substituents were varied in the series, trans-[NiX(2,3,5,6-C6F4I)(PEt2Ph)2] (X = F, I) 2pX. Crystal structures were obtained for the complete series 1pX, and for 1oF, 1oCl, 1oI and 2pI. All these complexes exhibited halogen bonds in the solid state, of which 1pF exhibited unique characteristics with a linear chain, the shortest halogen bond d(C6F4I···F-Ni) = 2.655(5) Å and the greatest reduction in halogen bond distance (I···F) compared to the sum of the Bondi van der Waals radii, 23%. The remaining complexes form zig-zag chains of halogen bonds with distances also reduced with respect to the sum of the van der Waals radii. The magnitude of the reductions follow the pattern F > Cl ? Br > I, 1pX > 1oX, consistent with the halogen bond strength following the same order. The variation in the I···X-Ni angles is consistent with the anisotropic charge distribution of the halide ligand. The temperature dependence of the X-ray structure of 1pF revealed a reduction in halogen bond distance of 0.055(7) Å on cooling from 240 to 111 K. Comparison of three polymorphs of 1oI shows that the halogen bond geometry may be altered significantly by the crystalline environment. The effect of the halogen bond on the 19F NMR chemical shift in the solid state is demonstrated by comparison of the magic-angle spinning NMR spectra of 1pF and 1oF with that of a complex incapable of halogen bond formation, trans-[NiF(C6F5)(PEt3)2] 3F. Halogen bonding causes deshielding of ?iso in the component of the tensor perpendicular to the nickel coordination plane. The results demonstrate the potential of fluoride ligands for formation of halogen bonds in supramolecular structures.

Dataset Information

Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0).

Publications

Small Phosphine Ligands Enable Selective Oxidative Addition of Ar-O over Ar-Cl Bonds at Nickel(0).

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