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Compound 1 is made up of two norbornane like P7 units coupled in a unique way. It results from thermolysis of a mixture of bi-and tri-cyclic isopropylphosphanes and represents the first tetradecaphosphane to be characterized structurally. According to 1H{31P} NMR data, the configurational isomer present in the crystalline phase equilibrates in solution with two diastereomers.