We present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via salt metathesis reactionof halophosphanes with metal phosphides in high yield. We vastly expanded this group of compounds by obtaining the first mono- and tri-amino-substituted systems. The structures of isolated compounds were characterized by NMR spectroscopy and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as a whole we conducted a DFT study on electronic and steric properties of obtained systems. The experimental and theoretical results can be very useful for designing P-P systems with desired properties.
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