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Linear free energy relationships (LFERs) were established for copper-catalyzed C(sp3)-X bond cleavage in alkyl halides. A multivariate linear regression model accurately predicts reaction rates for designing effective catalysts in atom transfer radical reactions.

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Area of Science:

  • Catalysis
  • Organic Chemistry
  • Physical Chemistry

Background:

  • Linear free energy relationships (LFERs) are crucial for predicting reaction outcomes and designing catalysts in chemical reactions.
  • Reductive cleavage of the C(sp3)-X bond in alkyl halides by copper (Cu) complexes is a key step in atom transfer radical polymerization and addition/cyclization reactions.

Purpose of the Study:

  • To establish LFERs for the reductive cleavage of C(sp3)-X bonds by Cu complexes.
  • To identify fundamental descriptors of Cu complexes and alkyl halides influencing reactivity.
  • To develop predictive models for reaction rate constants (kact).

Main Methods:

  • Established LFERs using the equation log kact = s(I + C + S) for 107 Cu complex/alkyl halide pairs across 5 solvents.
  • Correlated LFER parameters (I, C, S, s) with descriptors like bond dissociation free energy, Tolman cone angle, electron affinity, radical stabilization energy, redox potential, solvent polarizability, and distortion energy.
  • Employed multivariate linear regression (MLR) to develop a predictive model for kact.

Main Results:

  • LFERs effectively interpolated kact values spanning over 13 orders of magnitude.
  • Identified key descriptors influencing the reductive cleavage of C(sp3)-X bonds.
  • The MLR model demonstrated superior predictive capability over the LFER equation.
  • Predicted kact values for over 2000 Cu complex/alkyl halide pairs using the MLR model.

Conclusions:

  • The established LFERs and identified descriptors provide fundamental insights into the reactivity of Cu complexes and alkyl halides in C(sp3)-X bond cleavage.
  • The MLR model offers a powerful tool for predicting and optimizing catalyst performance in atom transfer radical reactions.
  • This work facilitates the rational design of novel catalytic systems for various radical-mediated transformations.