Polysilylamides (n = 1-8) with a Si-Cl functionality containing pentacoordinate silicon in the backbone were produced in high yield by transsilylation of bis(chloromethyl)methylchlorosilane and the trimethylsilyl derivative of diketopiperazine. Pentacoordinate polysilylamides were highly soluble in water as a result of silicon water coordination (Si←OH 2) from hydrolysis of the Si-Cl group in each repeat unit. Interestingly, the water silicon coordination in polysilanolamides was stable toward self-condensation and found to contain pentacoordinate silicon even in water, thus avoiding siloxane (Si-O-Si) bond formation. In the gas phase the polysilanolamides underwent intramolecular stepwise hydrolysis-condensation possibly as a result of C=C double-bond formation at each monomer unit, as observed by MALDI-TOF MS. Low-intensity peaks of macrocyclic polysilanolamides (n = 2-5) were also observed that contain water molecules. For a better understanding of the hydrolysis-condensation process of the polysilylamide, new model compounds of pentacoordinated silicon derivatives of pyridones were synthesized, characterized, and compared with the polysilanolamides using NMR and X-ray crystallography. X-ray analysis of the model compounds revealed insight into the silicon water coordination in each repeat unit and the mode of packing within the polymers that contain these monomer units. It is found that the partial hydrolysis of the model pentacoordinate chlorosilanes gives water-coordinated pentacoordinate silicon species that resemble an intermediate in the aqueous hydrolysis of pentacoordinate polysilylamides.
ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry