Metallomacrocycles incorporating a hemilabile Tröger's base derived ligand

Inorganic Chemistry
Meisa S KhoshbinArnold L Rheingold

Abstract

Tröger's base, a chiral molecule with a rigid 90 degrees backbone, has been incorporated into a novel hemilabile phosphinoalkyl thioether ligand. Using the Weak Link Approach, this ligand has been reacted with Cu(CH3CN)4PF6 and [Rh(COE)2Cl]x (COE = cyclooctene) to form metallomacrocycles. Upon reaction of the ligand with Cu(I), which prefers a tetrahedral coordination geometry, a bimetallic macrocycle was formed. Alternatively, owing to the steric restrictions imposed by the 90 degrees backbone of the ligand and the square-planar geometry of Rh(I), 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 Cu(I) complex causes the weak thioether-Cu bonds to break, generating a large bimetallic open macrocycle. Upon reaction of the mixture of Rh(I) 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 Rh(I) macrocyclic complexes has been analyzed using gel permeation chromatography, and the tetramer has...Continue Reading

References

Dec 14, 2001·Journal of the American Chemical Society·Y KuboY Ishimaru
Aug 28, 2003·Journal of the American Chemical Society·Nathan C GianneschiArnold L Rheingold
Oct 16, 2004·Angewandte Chemie·Nathan C GianneschiChad A Mirkin
Dec 31, 2004·Organic Letters·Bohumil DolenskýVladimír Král
Feb 1, 2005·Inorganic Chemistry·Meisa S KhoshbinArnold L Rheingold
Feb 11, 2005·Journal of the American Chemical Society·Nathan C GianneschiChad A Mirkin
Mar 2, 1998·Angewandte Chemie·Joshua R FarrellArnold L Rheingold

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Citations

Nov 26, 2008·Chemical Communications : Chem Comm·Brian H NorthropPeter J Stang
Mar 18, 2010·Chemical Communications : Chem Comm·Christophe MichonJérôme Lacour
Aug 23, 2017·Organic & Biomolecular Chemistry·Sankarasekaran ShanmugarajuThorfinnur Gunnlaugsson
Apr 19, 2007·Chemistry, an Asian Journal·Meisa S KhoshbinArnold L Rheingold
Jan 24, 2009·Chirality·Christophe MichonJérôme Lacour
May 8, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Arun Kumar BarPartha Sarathi Mukherjee
May 16, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Ján CvengrošNico Santschi
Jun 3, 2015·Journal of the American Chemical Society·Alejo M LifschitzChad A Mirkin

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