A series of novel neutral pentacoordinate silicon(IV) complexes with SiClSN(2)C, SiBrSN(2)C, SiSN(3)C, SiSON(2)C, SiS(2)N(2)C, SiSeSN(2)C and SiTeSN(2)C skeletons (compounds 1-12) was synthesised, starting from PhSiCl(3), PhSiBr(3), PhSi(NCO)(3), MeSiCl(3) or C(6)F(5)SiCl(3). 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, N(3), OS(O)(2)CF(3), 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.