N-Cyclohexylideneimino-O-(trimethylsilyl)acylimidates react smoothly with XSiCl3(X = Me, Ph, vinyl and Cl) in a transsilylation reaction producing ionic pentacoordinate bischelates and neutral hexacoordinated complexes depending on the electronic and steric behavior of the ligands. These hypercoordinated silicon complexes are characterized by UV-Vis, FT-IR and NMR spectroscopic techniques. A neutral hexacoordinate silicon complex with dichloro ligands was characterized by single crystal X-ray analysis. The UV-Vis absorption data showed a significant bathochromic shift of λmaxin hypercoordinated silicon complexes on comparison with their corresponding hydrazide ligands. The 29Si NMR chemical shifts strongly depend on nature of X group directly attached to the central silicon atom toward ionization. © 2014 Elsevier B.V. All rights reserved.