The syntheses of organohydridosilanes containing Y,C,Y-chelating ligands of the general formula PhL 1-3 SiH 2 (1, L 1 = C 6 H 3 (CH 2 O t Bu) 2 -2,6; 2, L 2 = C 6 H 3 (CH 2 O t Bu)-2-(CH 2 NMe 2 )-6; 3, L 3 = C 6 H 3 (CH 2 NMe 2 ) 2 -2,6) are reported. The reactivity of compounds 1–3 towards elemental sulphur and selenium was studied. It depends on the identity of the donor atoms. While the ether-substituted organohydridosilane PhL 1 SiH 2 (1) does not react, the amino-substituted organohydridosilanes PhL 2 SiH 2 (2) and PhL 3 SiH 2 (3) provide the N→Si-coordinated silathiones PhL 2 SiS (4), PhL 3 SiS (6) and the silaselenones PhL 2 SiSe (5), PhL 3 SiSe (7), respectively, all containing terminal Si–E bonds (E = S, Se). Compounds 1 and 2 do not react with water at ambient temperature whereas the hydrolysis of 3 yielded the diorganosilanediol PhL 3 Si(OH) 2 (8). The compounds are characterized by 1 H, 13 C, 29 Si, (1–8) and 77 Se (6, 7) NMR spectroscopy and single crystal X-ray diffraction analysis (1, 8). In addition, the vapour pressures of compounds 2 and 3 were determined as well.