{'fraction_non_alphanumeric': 0.020718232044198894, 'fraction_numerical': 0.003453038674033149, 'mean_word_length': 5.646788990825688, 'pattern_counts': {'":': 0, '<': 0, '<?xml version=': 0, '>': 0, 'https://': 0, 'lorem ipsum': 0, 'www.': 0, 'xml': 0}, 'pii_count': 0, 'substrings_counts': 0, 'word_list_counts': {'cursed_substrings.json': 0, 'profanity_word_list.json': 0, 'sexual_word_list.json': 0, 'zh_pornsignals.json': 0}}
Exploiting and Understanding the Selectivity of Ru-N-Heterocyclic Carbene Metathesis Catalysts for the Ethenolysis of Cyclic Olefins to α,ω-Dienes.

A library of 29 homologous Ru-based olefin metathesis catalysts has been tested for ethenolysis of cyclic olefins toward the goal of selectively forming α,ω-diene using cis-cyclooctene as a prototypical substrate. Dissymmetry at the N-heterocyclic carbene (NHC) ligand was identified as a key parameter for controlling the selectivity. The best-performing catalyst bearing an N-CF3 group significantly outperformed the benchmark second-generation Grubbs catalyst in the ethenolysis of cis-cyclooctene. Application of this optimal catalyst to the ethenolysis of various norbornenes allows the efficient synthesis of valuable diene intermediates in good yields. The observed ligand effect trends could be rationalized through univariate and multivariate parameter analysis involving steric and electronic descriptors of the NHC ligand in the form of the buried volume and the 77Se NMR chemical shift, in particular the σyy component of the shielding tensor of [Se(NHC)] model compounds, respectively. Natural chemical shift analysis of this chemical shielding tensor shows that σyy probes the π-acceptor property of the NHC ligand, the essential electronic parameter that drives the relative rate of degenerate metathesis and selectivity in ethenolysis with catalysts bearing dissymmetric NHC ligands.