Nickel-Catalyzed Alkyl Coupling Reactions: Evaluation of Computational Methods

Pratt, Lawrence M.; Voit, Stewart L; Okeke, Fabian N.; Kambe, Nobuaki

doi:10.1021/jp1077196

Cited by 29 publications

(19 citation statements)

References 29 publications

(44 reference statements)

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“…75 Also, in a study by Pratt et al, the authors observed that, relative to CCSD(T) reference data, B3LYP performed well and could successfully be employed for geometry optimization of reactants and intermediates in an alkyl coupling reaction with a small Ni complex (Figure 2b). 76 Similar conclusions were also obtained in a study by Hughes and co-workers who observed that B3LYP may perform well in reproducing experimental X-ray data of alkene−Ir(Cp) complexes ( Figure 2c). 77 Besides B3LYP, other popular methods such as BP86, B3PW91, and PBE0 have also shown acceptable and sometimes even better performance than B3LYP in reproducing crystallographic structural data of organometallic complexes.…”

Section: Geometry Optimizationssupporting

confidence: 87%

“…Examples of transition-metal complexes where accurate geometries may be obtained when employing the popular density DFT methods, such as B3LYP or other "dispersion-free" methods. [75][76][77]79 In this study, the organometallic complexes were either catalyst precursors or important intermediates in the catalytic processes, and by comparing the computational results with crystallographic data the authors observed that the DFT method that gave the best overall geometry optimization performance (with respect to statistical errors) was the dispersion-corrected DFT method ωB97X-D, whereas B3LYP was attributed with large statistical errors. However, as discussed in a study by Jacobsen and Cavallo, 84 one should not forget that dispersive interactions are often different in X-ray structures than in solution.…”

Section: Geometry Optimizationsmentioning

confidence: 95%

See 1 more Smart Citation

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

et al. 2015

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Section: Geometry Optimizationssupporting

confidence: 87%

Section: Geometry Optimizationsmentioning

confidence: 95%

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

et al. 2015

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“…This level of theory has been applied frequently to Pt‐ and Ni‐centered pincer complexes. Specifically, DFT/B3LYP has been used to model ground state geometries, molecular orbital energies and associated spectroscopic properties, and vibrational energies compared with infrared spectra . In each case, quantities predicted using DFT‐B3LYP agree well with empirical data.…”

Section: Introductionmentioning

confidence: 93%

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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“…9 Theoretical calculations regarding this pathway suggest the possibility of Ni(IV) intermediates (C). 10,11 If the reaction proceeds via C, although counter Mg cations may play important roles in the real system, the activation parameters shown in Table 2 correspond to this oxidative addition step, because the calculations suggest that the successive reductive elimination step is highly exergonic with a low energy barrier and so should be rapid, even at low temperatures. 10 Fu performed a kinetic study of the oxidative addition of alkyl halides to Pd(0) as a key step in Pd-catalyzed cross-coupling and revealed that activation parameters of the oxidative addition of nonyl bromide with Pd[P(t-Bu) 2 Me] 2 leading to n-C 9 H 19 PdBr[P(t-Bu) 2 12 It is interesting that reaction of a Pd complex with alkyl halides has a small activation enthalpy and is controlled by an entropy factor, while the reaction of the Ni complex (B) with alkyl halides is enthalpy-controlled.…”

Section: Rmgclmentioning

confidence: 99%

Kinetic Studies of the Ni-catalyzed Cross-coupling of Alkyl Halides and a Tosylate with Butyl Grignard Reagent in the Presence of 1,3-Butadiene

Iwasaki¹,

Tsumura²,

Omori³

et al. 2011

Chemistry Letters

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Kinetic studies of the nickel-catalyzed cross-coupling reaction of alkyl bromides, iodides, and tosylates with butyl Grignard reagents in the presence of butadiene were performed. The reaction rate was first order with respect to the halides and the nickel catalyst. The butyl Grignard reagent, at concentrations of ca. 0.4 M or higher, had little effect on the reaction rate. The relative reactivities and activation parameters were determined for these alkyl halides and a tosylate.Cross-coupling reactions are useful and powerful tools for connecting two different organic moieties via a single bond and have been widely employed in organic synthesis.1 During the past decade, the scope of this cross-coupling has been expanded to the use of alkyl halides as a coupling partner.2 In a previous study, we reported that nickel as well as palladium and copper showed unique catalytic activities for cross-coupling reactions in which alkyl halides were used in the presence of a ³-carbon ligand such as 1,3-butadiene or an alkyne.3 The Ni/butadiene system (eq 1) showed particularly high performance, allowing the selective alkylalkyl cross-coupling of alkyl halides with a Grignard reagent 4 in the presence of various functional groups. 5 Furthermore, the turn-over number can reach the order of 10 7 . 6 In order to probe this reaction in more detail, we performed kinetic studies and report on the results obtained.We first examined the time course for the reaction of nonyl bromide (1a) with excess butyl Grignard reagent using various Ni salts and 1,3-butadiene in THF at 0°C. As shown in Figure 1, all of the Ni salts afforded tridecane (3a) exclusively in quantitative yield based on the bromide within 15 min, but an induction period was observed for several salts probably due to their low solubilities in THF. NiBr 2 /dme (dme: dimethoxyethane) and [Ni(acac) 2 ] did not show any apparent induction period. Therefore, we used NiBr 2 /dme as the source of the Ni catalyst throughout this kinetic study.We then examined order of the rate for each reagent. A reaction using NiBr 2 /dme, similar to that of Figure 1 was performed using different concentrations of nonyl bromide (1a) at ¹35°C and the reaction was quenched with 1 M HCl(aq) after stirring for 90 s. These results were plotted in Figure 2 and a good straight line was obtained, indicating that this reaction obeys first-order kinetics with respect to nonyl bromide with a pseudofirst-order rate constant k obs = 1.76 © 10 ¹3 s ¹1 for r = k obs [n-C 9 H 19 Br].The effect of the catalyst and Grignard reagent on the reaction rate was examined using heptyl tosylate (1b) at 1°C for 150 s. In a similar manner, the yield of undecane (3b) was plotted against the concentration of the Ni catalyst employed, and the results are shown in Figure 3. These data clearly indicate that the reaction rate is first order with respect to the catalyst concentration.When we ran the same reaction using different concentrations of n-BuMgCl, an interesting result was obtained (Figure 4). The reaction was accelerat...

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Nickel-Catalyzed Alkyl Coupling Reactions: Evaluation of Computational Methods

Cited by 29 publications

References 29 publications

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

Computational Studies of Synthetically Relevant Homogeneous Organometallic Catalysis Involving Ni, Pd, Ir, and Rh: An Overview of Commonly Employed DFT Methods and Mechanistic Insights

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

Kinetic Studies of the Ni-catalyzed Cross-coupling of Alkyl Halides and a Tosylate with Butyl Grignard Reagent in the Presence of 1,3-Butadiene

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