Generation of MoNo- and bimetallic palladium complexes and mechanistic insight into an operative metal ring-walking process

Meital Orbach, Sreejith Shankar, Olena V. Zenkina, Petr Milko, Yael Diskin-Posner, Milko E. Van Der Boom

Research output: Contribution to journalArticle

6 Citations (Scopus)


This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast n2-C - C coordination of only one Pd(PEt3)2 moiety, which then significantly slows down the subsequent reaction. Electronic effects induced by complexation of the first metal center have a major effect on the subsequent formation of the bimetallic complexes. These effects are reduced by partial fluorination of the bis(vinylpyridine)-arene ligand. The monometallic complexes display migration of the Pd(PEt3)2 moiety between the two olefinic bonds of the corresponding ligand, as indicated by various solution NMR experiments, including variable-temperature NMR spectroscopy, 2D 1H-1H exchange spectroscopy, and spin saturation transfer. Density functional theory studies were performed at the SMD(toluene)-PBE0+d(v3)/B2//B97D/B1 level of theory.

Original languageEnglish
Pages (from-to)1098-1106
Number of pages9
Issue number6
Publication statusPublished - Mar 23 2015


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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