Bidentate intermolecular Si...N interactions were utilized to form new hypervalent complexes of trifluoro-phenylethynyl-silane with 2,2'-bipyridine and with 1,10-phenanthroline. X-ray structures obtained for these complexes display a somewhat distorted octahedral geometry about the silicon atom. Binding constants ranging from 170 to 1600 M-1 at 25 degreesC in CDC1(3) were measured for the formation of these complexes, suggesting that such hypervalent complexes of silicon could be used as new motifs in supramolecular chemistry.