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Abstract
The incorporation of main-group elements into macrocycles leads to stabilization of novel structures and control of reactivity. The tetraamino macrocycle cyclen appears to favor a pentacoordinate trigonal bipyramidal (tbp) geometry about phosphorus, even when phosphorus is bonded to transition-metals. The tbp geometry is also favored for arsenic. The tetraphenol macrocycle p-tert-butylcalix[4]arene appears to stabilize a hexacoordinate phosphorus geometry under certain conditions; however, pentacoordinate and tricoordinate structures are also found.
