One-pot generation of a tris-cationic homobimetallic planar-chiral ruthenacycle

Jean Pierre Djukic, Ludivine Fetzer, Andrew Czysz, Wissam Iali, Claude Sirlin, Michel Pfeffer

Research output: Contribution to journalArticlepeer-review

Abstract

The "one-pot" generation of a tris-cationic homobimetallic racemic planar-chiral ruthenacyclic ruthenium sandwich complex from a reaction of the metal-free chelating ligand with the (-6-benzene) dichloridoruthenium(II) dimer in acetonitrile is reported. This unexpected complex, which was characterized by structural X-ray diffraction analysis, is the product of a multistep process entailing first the cycloruthenation of the ligand, a ligand exchange reaction, and eventually the site-selective π-bonding of a bis-cationic [(-6-benzene)Ru]2+ moiety to a monocationic ruthenacyclic intermediate. Investigations of the underlying electronic structure and bonding scheme by resorting to quantum chemical methods of the density functional theory have revealed the key role played by the electron-donating NMe2 substituent, which enables the a priori antagonistic π-coordination of the in situ-formed cationic ruthenacycle by a dicationic (-6-arene) ruthenium(II) moiety. Experimental evidence indicates indeed that, in the absence of such an electron-donating group at the metalacycle, the π-coordination of the [(-6-benzene)Ru] 2+ cannot take place.

Original languageEnglish (US)
Pages (from-to)1675-1679
Number of pages5
JournalOrganometallics
Volume29
Issue number7
DOIs
StatePublished - Apr 12 2010
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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