A series of novel neutral pentacoordinate silicon(IV) complexes with SiClSN₂C, SiBrSN₂C, SiSN₃C, SiSON₂C, SiS₂N₂C, SiSeSN₂C and SiTeSN₂C skeletons (compounds 1–12) was synthesised, starting from PhSiCl₃, PhSiBr₃, PhSi(NCO)₃, MeSiCl₃ or C₆F₅SiCl₃. Compounds 1–12 contain (i) a tridentate dianionic N,N,S chelate ligand (derived from 2-{[(pyridin-2-yl)methyl]amino}benzenethiol), (ii) a phenyl, methyl or pentafluorophenyl group and (iii) a monodentate monoanionic ligand (Cl, Br, NCO, NCS, N₃, OS(O)₂CF₃, OPh, SPh, SePh, TePh). The pentacoordinate silicon(IV) complexes 1–12 were characterised by elemental analyses, NMR spectroscopic studies in the solid state and in solution and crystal structure analyses. These experimental investigations were complemented by computational studies.