New diazaphospholes and diazaphosphorinanes (1–12) were synthesized and characterized by 1H, 13C, 31P NMR, mass and IR spectroscopy and elemental analysis. The factors which affect the 2,3J(P,X) (X@H, C) coupling constants in compounds 1–12 were considered. The ring size and the hybridization are parameters which change the 2J(PNH) coupling constant in the sequence benzodiazaphospholes > diazaphospholes > diazaphosphorinanes. Also, attention was paid to exocyclic substituent effects. Asymmetric diazaphospholes 5–8 indicate two different 2J(P,C)aliphatic values, and the more deshielded carbon atom has a higher coupling constant. The crystal structures of compounds 7 and 10–12 were determined by X-ray crystallography. Hydrogen bonds produce a 2D framework for compound 10, which is composed of two symmetrically independent molecules. Compounds 7, 11 and 12 exist as a polymeric chain, 2D framework and centrosymmetric dimer, respectively, which are made by hydrogen bonds.

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