caa a22 4500 605513368 CHVBK 20210128100659.0 cr unu---uuuuu 210128e20150501xx s 000 0 eng 10.1007/s00894-015-2672-7 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2672-7 Mechanisms for the synthesis of conjugated enynes from diphenylacetylene and trimethylsilylacetylene catalyzed by a nickel(0) complex: DFT study of ligand-controlled selectivity [Elektronische Daten] [Cheng Huang, Rongxing He, Wei Shen, Ming Li] Density functional theory (DFT) was utilized to elucidate the reaction mechanisms of and the key factors that influence the Ni(0)-catalyzed cross-dimerization and -trimerization of trimethylsilylacetylene (R1) and diphenylacetylene (R2). Calculated results revealed that the electron-donating ability of the ligand plays a crucial role in determining the regionselectivity of this tandem reaction. The use of strongly electron-donating ligands favors the formation of cross-dimer intermediates, whereas cross-trimer products can easily be synthesized using weakly electron-donating ligands. A simple method of estimating the electron-donating abilities of different ligands based on the Mulliken charge distribution of the ligand-ligand pair was employed. The present theoretical results allow us to elucidate the reaction mechanisms for and to identify the factors that exert the greatest influence on the ligand-controlled cross-dimerization and -trimerization of trimethylsilylacetylene and diphenylacetylene. Guidelines for the design of novel ligand systems with Ni(0) catalysts are also proposed. Graphical Abstract The electron-donating abilities of two different ligands Springer-Verlag Berlin Heidelberg, 2015 Diphenylacetylene nationallicence Trimethylsilylacetylene nationallicence DFT nationallicence Ligand nationallicence Selectivity nationallicence Huang Cheng School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut He Rongxing School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut Shen Wei School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut Li Ming School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-15 1610-2940 21:5<1 2015 21 894 https://doi.org/10.1007/s00894-015-2672-7 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2672-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Huang Cheng School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut NATIONALLICENCE 700 1- He Rongxing School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut NATIONALLICENCE 700 1- Shen Wei School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut NATIONALLICENCE 700 1- Li Ming School of Chemistry and Chemical Engineering, Southwest University, 400715, Chongqing, China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-15 1610-2940 21:5<1 2015 21 894