Metallomacrocycles incorporating a hemilabile Tröger's base derived ligand

Meisa S. Khoshbin, Maxim V. Ovchinnikov, Chad A. Mirkin*, James A. Golen, Arnold L. Rheingold

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

28 Scopus citations

Abstract

Tröger's base, a chiral molecule with a rigid 90° backbone, has been incorporated into a novel hemilabile phosphinoalkyl thioether ligand. Using the Weak Link Approach, this ligand has been reacted with Cu(CH 3CN)4PF6 and [Rh(COE)2Cl] x (COE = cyclooctene) to form metallomacrocycles. Upon reaction of the ligand with CuI, which prefers a tetrahedral coordination geometry, a bimetallic macrocycle was formed. Alternatively, owing to the steric restrictions imposed by the 90° backbone of the ligand and the square-planar geometry of RhI, when the ligand was reacted with [Rh(COE)2Cl]x, the formation of bimetallic closed macrocycles was not observed, and instead a mixture of tri- and tetrametallic closed macrocycles is formed. Introducing pyridine to the CuI complex causes the weak thioether-Cu bonds to break, generating a large bimetallic open macrocycle. Upon reaction of the mixture of RhI metallomacrocycles with CO and Cl-, the cyclic structure of these complexes becomes flexible enough that the dimeric bimetallic macrocycle forms, along with tri- and tetrameric open complexes. The mixture of differently sized RhI macrocyclic complexes has been analyzed using gel permeation chromatography, and the tetramer has been characterized by a single-crystal X-ray diffraction study. These are the first examples of metallomacrocycles containing a Tröger's base derivative.

Original languageEnglish (US)
Pages (from-to)2603-2609
Number of pages7
JournalInorganic chemistry
Volume45
Issue number6
DOIs
StatePublished - Mar 20 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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