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 language | English (US) |
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Pages (from-to) | 2603-2609 |
Number of pages | 7 |
Journal | Inorganic chemistry |
Volume | 45 |
Issue number | 6 |
DOIs | |
State | Published - Mar 20 2006 |
ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
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CCDC 604385: Experimental Crystal Structure Determination
Khoshbin, M. S. (Creator), Ovchinnikov, M. V. (Creator), Mirkin, C. A. (Creator), Golen, J. A. (Creator) & Rheingold, A. L. (Creator), Cambridge Crystallographic Data Centre, 2006
DOI: 10.5517/ccn8x93, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccn8x93&sid=DataCite
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