Complexation studies of eleven N-heteroaromatic cations with tetraphenylborate are reported. Tetraphenylborate forms complexes with five cations and reacts to form Lewis-base boranes with six cations. The complexes and the displacement reaction products were characterised by 1 H NMR spectroscopy, elemental analysis and crystallographic methods. In the complexes C-H ؒ ؒ ؒ π or N-H ؒ ؒ ؒ π hydrogen bonds are the principal intermolecular interactions. The stability constants for the complexes are determined by 1 H NMR titration in acetonitrile-methanol (1 : 1) solution. Crystal structures of four of the complexes and three of the Lewis-base triphenylborane products are reported.
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