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Abstract
Single crystal X-ray diffraction studies of the macrocyclic bis(bicyclophosphoranes), [N(CH2)CMe2O)2PO2]2[(CH2)2S(CH2)2] (1) and [N-(CH2CMe2O)2PO2]2[(CH2)2 NPh(CH2)2][(CH2)2N-tBu(CH2)2] (2). revealed trigonal bipyramidal structures at the phosphorus atom. A comparison is made with the structures of related bicyclic phosphoranes containing similar ring systems that comprise both saturated (1–4) and unsaturated (5–8) members. A molecular mechanics treatment is performed which shows close agreement between the calculated and X-ray structures of 1 and 2.