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Synthesis and hydrolysis–condensation study of water-soluble self-assembled pentacoordinate polysilylamides

Synthesis and hydrolysis–condensation study of water-soluble self-assembled pentacoordinate polysilylamides
Synthesis and hydrolysis–condensation study of water-soluble self-assembled pentacoordinate polysilylamides
Polysilylamides (n = 1-8) with a Si-Cl functionality containing pentacoordinate silicon in the backbone were produced in high yield by transsilylation of bis(chloromethyOmethylchlorosilane and the trimethylsilyl derivative of diketopiperazine. Pentaco ordinate polysilylamides were highly soluble in water as a result of silicon water coordination (Si <- OH2) 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.
0276-7333
1721-1731
Sohail, Muhammad
ecac76ab-d63a-4f0a-a233-a7fa1e6cca1c
Bassindale, Alan R.
285ee4e0-58d0-4178-a0d9-d7e0d1efbebd
Taylor, Peter G.
e59508fd-4cfb-422c-bbb0-b70cfb6aa195
Korlyukov, Alexander A.
2456dc2b-9244-4a01-9e40-acb838822e93
Arkhipov, Dmitry E.
d66fa62a-99a0-4509-bf4e-1add89f241ff
Male, Louise
89b88c4f-2308-4b94-8f3a-2dc537a66533
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Sohail, Muhammad
ecac76ab-d63a-4f0a-a233-a7fa1e6cca1c
Bassindale, Alan R.
285ee4e0-58d0-4178-a0d9-d7e0d1efbebd
Taylor, Peter G.
e59508fd-4cfb-422c-bbb0-b70cfb6aa195
Korlyukov, Alexander A.
2456dc2b-9244-4a01-9e40-acb838822e93
Arkhipov, Dmitry E.
d66fa62a-99a0-4509-bf4e-1add89f241ff
Male, Louise
89b88c4f-2308-4b94-8f3a-2dc537a66533
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Sohail, Muhammad, Bassindale, Alan R., Taylor, Peter G., Korlyukov, Alexander A., Arkhipov, Dmitry E., Male, Louise, Coles, Simon J. and Hursthouse, Michael B. (2013) Synthesis and hydrolysis–condensation study of water-soluble self-assembled pentacoordinate polysilylamides. Organometallics, 32 (6), 1721-1731. (doi:10.1021/om301137b).

Record type: Article

Abstract

Polysilylamides (n = 1-8) with a Si-Cl functionality containing pentacoordinate silicon in the backbone were produced in high yield by transsilylation of bis(chloromethyOmethylchlorosilane and the trimethylsilyl derivative of diketopiperazine. Pentaco ordinate polysilylamides were highly soluble in water as a result of silicon water coordination (Si <- OH2) 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.

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Published date: 25 March 2013
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

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Local EPrints ID: 362495
URI: http://eprints.soton.ac.uk/id/eprint/362495
ISSN: 0276-7333
PURE UUID: 421b48e4-bda9-4b37-bf46-5870a622e266
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 25 Feb 2014 14:45
Last modified: 18 Feb 2021 16:53

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Contributors

Author: Muhammad Sohail
Author: Alan R. Bassindale
Author: Peter G. Taylor
Author: Alexander A. Korlyukov
Author: Dmitry E. Arkhipov
Author: Louise Male
Author: Simon J. Coles ORCID iD

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