Abstract
AbstractThe 1,4‐addition of diamine dinucleophiles to dimetalliccarbene scaffolds 5 yields tetrametallic azamacrocycles 9 and 10 with exocyclic metal–carbene nuclei, in excellent yields and with high stereocontrol. All‐Z stereoisomers are isolated in all cases, with the exception of the tungsten(0) macrocycle 10, which is obtained as a mixture of isomers. This methodology allows the preparation of a new type of homo‐ and heterocyclophane metallomacrocycles in which the geometry and the size of the cavity can be designed as a function of the biscarbene complexes employed and the diamines used as linkers. The X‐ray structure of complex 10a showing the high stability of the Z configuration of these compounds and the electrochemistry of the metallomacrocycles prepared are also reported.
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