Density functional study of possible intermediates in the mechanism of olefin cyclopropanation catalyzed by metal carboxylates

Cristóbal Rodríguez-García, Òscar González-Blanco, Antonio Oliva, Rosa M. Ortuño, Vicenç Branchadell

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15 Citations (Scopus)

Abstract

The structures of several complexes arising from the interaction between methylene and palladium and rhodium diformates were optimized through density functional calculations. For palladium, mono-, di-, and trimeric complexes were considered. The results obtained show that in all cases the most stable structures correspond to complexes in which methylene has inserted in one of the M-O bonds, while metal-carbene complexes are energy minima only for monomeric palladium diformate and for rhodium diformate. Trimeric palladium formate is thermodynamically stable upon fragmentation. However, when it reacts with methylene, fragmentation becomes favorable. The role of the resulting monomeric complex in the olefin cyclopropanation mechanism catalyzed by palladium dicarboxylates is discussed.
Original languageEnglish
Pages (from-to)1073-1078
JournalEur. J. Inorg. Chem.
Issue number5
DOIs
Publication statusPublished - 1 Jan 2000

Keywords

  • Carbene complexes
  • Carboxylato complexes
  • Density functional calculations
  • Palladium
  • Rhodium

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