Stable in the solid state and isolable in high yields are adducts of H2SiCl2, HSiCl3, and RSiCl3 (R = Me, Ph) with the N, N'-chelating ligands 1,10-phenanthroline (phen; 1c), 2,2-bipyridine (bipy; 1b), and (to a limited extent) N,N,N', N'-tetramethylethylenediamine (tmeda; 1 a). The products were comprehensively characterized via multinuclear solution and solid-state NMR spectroscopy, including analysis of the Si-29 NMR chemical shift anisotropy tensors, Raman spectroscopy, elemental analyses, and, for SiCl4(phen) (2c), HSiCl3(bipy) (3b), H2SiCl2(bipy) (4b), MeSiCl3(phen) (5c), and PhSiCl3(phen) (6c), single-crystal X-ray structure analyses. The latter revealed that the nonchlorine substituents (i.e., H, Me, and Ph) are exclusively trans-disposed to the N-donor atoms of the chelating ligands. A dismutation of the complexes HXSiC12(bipy) and HXSiCl2(tmeda) (X = H or Cl) was observed in polar solvents at elevated temperatures. This reaction is more pronounced when phen is used instead of bipy or tmeda. For MeHSiCl2(phen), in addition to undergoing H-Cl redistribution accompanied by the formation of 5c, an unexpected 1,4-hydrosilylation was observed. The latter was proven NMR-spectroscopically and by a single-crystal X-ray structure analysis of the product MeSiCl2(4H-phen) (7), a pentacoordinated silicon compound with a trigonal-bipyramidal arrangement of the subsituents and the methyl group located in an equatorial position.