Computational assessment of electron density in metallo-organic nickel pincer complexes for formation of PC bonds

Eller, Joshua J.; Downey, Karen

doi:10.1002/jcc.24034

Cited by 5 publications

(8 citation statements)

References 25 publications

(38 reference statements)

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“…Togni and co‐workers identified a Lewis acidic interaction between a PPP–Ni II pincer complex and the electron‐deficient olefin substrate . On the other hand, purely theoretical investigations in the absence of experimental support by Downey and co‐workers led to an alternative mechanism in which the active Ni–PPh 2 catalytic species was generated by displacing the Ni−Cl bond of the POCOP Ni II –Cl pre‐catalyst . Notably, direct participation of the Ni II center was involved in both proposed catalytic cycles and the active catalytic species were only generated in situ under reaction conditions.…”

Section: Resultsmentioning

confidence: 99%

Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction

Tay

Yang

et al. 2019

Chemistry A European J

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Synthetic challengesh ave significantly slowed the development of the catalytic asymmetrich ydroarsination reaction despite it being ah ighly attractive CÀAs bond formation methodology.Ina ddition, there is ap oor understanding of the main reactions teps in such reactions which limit further developmenti nt he field.H erein, key intermediates of the hydroarsination reactionc atalyzed by aP CP Ni II -Cl pincer complex are presentedu pon investigating the reactionw ith DFT calculations, conductivity measurements, NMR spectros-copy,a nd catalytic screening.T he novel Ni-Cl-As interaction proposed was then contrasted against known Ni II -catalyzed hydrophosphination reactions to highlight dissimilaritiesb etweent hem even though Pa nd As share ac lose group relationship. Lastly,t he asymmetrich ydroarsination of nitroolefins was further developed to furnish al ibrary of chiral organoarsines in up to 99 %y ield and 80 % ee under mild conditions (À20 8CtoR T) between 5t o2 10 mins.[a] W.Product 5b:White solid;the ee was determined on aDaicel Chiralpak ID column with n-hexane/2-propanol = 99:1, flow = 0.8 mL min À1 ,w avelength = 254 nm;r etention times:8 .7 (minor), 9.6 min (major); 1 HNMR (CD 3 CN, 500 MHz): d = 7. 15 H, Ar), 4.98 (dd, 1H, 3 J HH = 13.1, 3 J HH = 13.1 Hz, AsCH), 4.62 (dd, 1H, 3 J HH = 13.6, 2 J HH = 3.8 Hz, NCH), 4.38 ppm (dd, 1H, 3 J HH = 12.6 Hz, 2 Conflict of interestThe authors declare no conflict of interest.

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Section: Resultsmentioning

confidence: 99%

Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction

Tay

Yang

et al. 2019

Chemistry A European J

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“…Previous work using nickel‐based complexes confirmed that these complexes are relatively insensitive to solvent dielectric constant and to the chemical character of the monodentate ligand in terms of electron distribution and molecular orbital energies. It also showed that density functional theory (DFT) was the most accurate modeling approach for modeling this family of complexes . It did not, however, include analysis of the available functionals for use within DFT, instead considering only DFT‐B3LYP.…”

Section: Introductionmentioning

confidence: 93%

“…Because the precursor complexes are of interest for rapid generation of catalysts via ligand exchange, a key consideration is the presence of energetically accessible electron density centered on the metal cation. [15] Alternatively, the incoming phosphine ligand may bond to the metal center by donating electrons to the precursor complex lowest unoccupied molecular orbital (LUMO), in the case that the LUMO offers significant involvement at the metal center. Therefore, for each precursor complex, the highest unoccupied molecular orbital (HOMO) and LUMO were characterized ( Table 4) in terms of electron density at the center of the complex.…”

Section: Electron Distributionmentioning

confidence: 99%

“…It also showed that density functional theory (DFT) was the most accurate modeling approach for modeling this family of complexes. [15] It did not, however, include analysis of the available functionals for use within DFT, instead considering only DFT-B3LYP. This level of theory has been applied frequently to Pt-and Ni-centered pincer complexes.…”

Section: Introductionmentioning

confidence: 99%

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Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

Ellis

Downey

2016

Int J of Quantum Chemistry

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New group 10 metalloorganic complexes are proposed as the basis of new catalysts for the formation of carbon‐phosphorous bonds. Density functional theory (DFT) is applied, using multiple DFT functionals, to model molecular geometry as well as electron density distribution in the highest occupied molecular orbitals (HOMOs) expected to carry out a reductive catalytic cycle. DFT/M06 analysis predicts a robust planar geometry, regardless of alteration of major components. Precursors for rapid catalyst generation should begin with an electron‐withdrawing monodentate ligand. Palladium and platinum catalysts have lower chemical hardness, but the electron distribution in the HOMO of the nickel‐based catalyst is preferred for reductive catalytic mechanisms. Both electron density and chemical hardness, however, are affected by the choice of metal ion and the composition of the monodentate ligand bound to it. Group 10 metalloorganic complexes are modeled as precursors for generating new catalysts for a minimally wasteful method of forming bonds commonly found in biochemically active compounds. Suitable precursors have an accessible metal center, as well as significant the HOMO/LUMO involvement at the metal center. All complexes studied offer similar geometries, but precursor transformation into catalyst depends on the electron‐withdrawing ligand being exchanged. Catalyst turn over number is predicted to depend primarily on the central metal. © 2016 Wiley Periodicals, Inc.

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“…[14,100] A computational assessment of electron density in a nickel pincer complex (Figure 57) with respect to the formation of P-C bonds was performed by Downey and coworkers. [101] The DFT analysis depicted electron density at metal centers suitable for catalyzing bond formation in a proposed, reductive hydrophosphination mechanism. Pincer complexes were shown to be insensitive to solvent dielectric constants through the orbital energies and consequently the HOMO-LUMO gap.…”

Section: Beletskayamentioning

confidence: 99%

Metal-Catalyzed Hydrophosphination

Novas

Waterman

2022

Preprint

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Organophosphines have garnered attention from many avenues ranging from agriculture to fine chemicals. One-time use of phosphate resources has made sustainable use of phosphorus overall imperative. Hydrophosphination serves as an efficient method to selectively prepare P–C bonds, furnishing a range of phosphorus-containing molecules while maximizing the efficient use of phosphorus. Since its discovery in the 1990s, a wide array of catalysts have appeared for hydrophosphination, a reaction that is spontaneous in some instances. This review presents a representative view of the literature based on known catalysts through mid-2022, highlighting extensions to unique substrates and advances in selectivity. While several excellent reviews have appeared for aspects of this transformation, this review is meant as a comprehensive guide to reported catalysts.

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Computational assessment of electron density in metallo-organic nickel pincer complexes for formation of PC bonds

Cited by 5 publications

References 25 publications

Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction

Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction

Density functional analysis of group 10 organometallic diphosphinito complexes for catalytic formation of C‐P bonds

Metal-Catalyzed Hydrophosphination

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