Metallomacrocycles Incorporating a Hemilabile Tröger's Base Derived Ligand

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• 作者：Meisa S. Khoshbin ; Maxim V. Ovchinnikov ; Chad A. Mirkin ; James A. Golen ; and Arnold L. Rheingold
• 刊名：Inorganic Chemistry
• 出版年：2006
• 出版时间：March 20, 2006
• 年：2006
• 卷：45
• 期：6
• 页码：2603 - 2609
• 全文大小：213K
• 年卷期：v.45,no.6(March 20, 2006)
• ISSN：1520-510X

文摘

Tröger's base, a chiral molecule with a rigid 90ages/entities/deg.gif"> backbone, has been incorporated into a novel hemilabilephosphinoalkyl thioether ligand. Using the Weak Link Approach, this ligand has been reacted with Cu(CH₃CN)₄PF₆and [Rh(COE)₂Cl]_x (COE = cyclooctene) to form metallomacrocycles. Upon reaction of the ligand with Cu^I, whichprefers a tetrahedral coordination geometry, a bimetallic macrocycle was formed. Alternatively, owing to the stericrestrictions imposed by the 90ages/entities/deg.gif"> backbone of the ligand and the square-planar geometry of Rh^I, when the ligandwas reacted with [Rh(COE)₂Cl]_x, the formation of bimetallic closed macrocycles was not observed, and instead amixture of tri- and tetrametallic closed macrocycles is formed. Introducing pyridine to the Cu^I complex causes theweak thioether-Cu bonds to break, generating a large bimetallic open macrocycle. Upon reaction of the mixtureof Rh^I metallomacrocycles with CO and Cl^-, the cyclic structure of these complexes becomes flexible enough thatthe dimeric bimetallic macrocycle forms, along with tri- and tetrameric open complexes. The mixture of differentlysized Rh^I macrocyclic complexes has been analyzed using gel permeation chromatography, and the tetramer hasbeen characterized by a single-crystal X-ray diffraction study. These are the first examples of metallomacrocyclescontaining a Tröger's base derivative.