Unexpected Conformational Behaviour of a Diphosphate Derived from a Spherand-Type Calixarene

The spherand-type calixarene 2a, which consists of three diphenol units linked by methylene bridges, was treated with phosphorus pentachloride and then with water. A C1-symmetrical conformation was found for the resulting bisphosphate 7 in the crystalline state by X-ray analysis, with an anti orientation of the phosphoryl groups. MM3 calculations lead to a nearly identical conformation for the most stable isomer (RRS-twist), while a slightly higher energy was found for an RRS-crown isomer with a syn orientation of the phosporyl groups. Surprisingly, all NMR studies (1H, 13C and 31P) of 7 are in agreement with a dynamic C2 symmetry in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Wein…