Tr&
ouml;ger's base, a chiral molecule with a rigid 90
![](/images/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(CH
3CN)
4PF
6and [Rh(COE)
2Cl]
x (COE = cyclooctene) to form metallomacrocycles. Upon reaction of the ligand with Cu
I, whichprefers a te
trahedral coordination geome
try, a bimetallic macrocycle was formed. Alternatively, owing to the stericres
trictions imposed by the 90
![](/images/entities/deg.gif)
backbone of the ligand and the square-planar geome
try 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 te
trametallic closed macrocycles is formed. In
troducing 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 s
tructure of these complexes becomes flexible enough thatthe dimeric bimetallic macrocycle forms, along with
tri- and te
trameric open complexes. The mixture of differentlysized Rh
I macrocyclic complexes has been analyzed using gel permeation chromatography, and the te
tramer hasbeen characterized by a single-crystal X-ray diffraction study. These are the first examples of metallomacrocyclescontaining a Tr&
ouml;ger's base derivative.