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 van der Boom

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

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
JournalOrganometallics
Volume34
Issue number6
DOIs
Publication statusPublished - Mar 23 2015

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walking
Palladium
palladium
Metals
Ligands
ligands
rings
metals
Fluorination
nuclear magnetic resonance
fluorination
Surface mount technology
Toluene
Complexation
spectroscopy
Nuclear magnetic resonance spectroscopy
Density functional theory
toluene
reactivity
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Generation of MoNo- and bimetallic palladium complexes and mechanistic insight into an operative metal ring-walking process. / Orbach, Meital; Shankar, Sreejith; Zenkina, Olena V.; Milko, Petr; Diskin-Posner, Yael; van der Boom, Milko.

In: Organometallics, Vol. 34, No. 6, 23.03.2015, p. 1098-1106.

Research output: Contribution to journalArticle

Orbach, Meital ; Shankar, Sreejith ; Zenkina, Olena V. ; Milko, Petr ; Diskin-Posner, Yael ; van der Boom, Milko. / Generation of MoNo- and bimetallic palladium complexes and mechanistic insight into an operative metal ring-walking process. In: Organometallics. 2015 ; Vol. 34, No. 6. pp. 1098-1106.
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