Reductive Elimination or C−C Bond Activation with Model Ni, Pd, Pt Complexes? A High‐Accuracy Comparative Computational Analysis of Reactivity

Abstract

The development of Pd-and Ni-catalyzed reactions for CÀ C bond formation is one of the primary driving forces in modern organic synthesis and the fine chemical industry. However, understanding the role of conformational mobility in reaction mechanisms is a long-standing challenge. We highlight the effect of a multirotamer (multiconformer) system on the effective Gibbs free energy of activation in the key CÀ C coupling process and promote the use of a simplified version of multiconformer transition state theory that is straightforward to apply. Multivariate regression helped to quantitatively map the effect of coupled organic substituents (their structural and electronic parameters), as well as to determine the relative activity of metals. We provide computational evidence for solvent control of the equilibrium in RE/CÀ C-bond activation for some model complexes. We also demonstrate that Ni complexes, being unique in the catalysis of sp 3 -sp 3 couplings, can be more challenging for machine learning and computational chemistry. The modeling was performed at an exceptionally high level, DLPNO-CCSD(T)/CBS//RIJCOSX-PBE0-D4/def2-TZVP. The Conclusions section contains an infographic summarizing the key findings related to the fields of cross-coupling catalysis, machine learning in catalysis, and computational chemistry.

From Synthesis Conditions to UiO-66 Properties: Machine Learning Approach

“…This can potentially compromise the predictive accuracy of ML models when data quality is paramount . Notably, studies suggest that expansive data sets are not invariably essential for achieving commendable predictive accuracy in ML models. ,, …”

“…42 Notably, studies suggest that expansive data sets are not invariably essential for achieving commendable predictive accuracy in ML models. 117,107,108 During the data compilation process, we focused on obtaining detailed information regarding both the synthesis conditions and the resultant properties of UiO-66. For synthesis conditions, we recorded the concentrations of all reaction mixture reagents (ZrCl 4 or ZrOCl 2 •8H 2 O, terephthalic acid, modulator amount, and water), along with the temperature and duration of synthesis.…”

Will We Witness Enzymatic or Pd-(Oligo)Peptide Catalysis in Suzuki Cross-Coupling Reactions?

“…We used SMD to account for solvation effects following a previous work . Single-point calculations were performed using the B3LYP functional − with the 6-31G* basis set. , For Pd, we selected the LANL2DZ basis set because of the absence of the parameters in 6-31G*.…”

1,2,4‐Triazines and Calcium Carbide in the Catalyst‐Free Synthesis of 2,3,6‐Trisubstituted Pyridines and Their D‐, 13C‐, and Doubly D2‐13C2‐Labeled Analogues

“…The authors have cited additional references within the Supporting Information (Ref. [42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60]).…”