The Nature of Hydrogen Bonding Involving the Siloxane Group

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doi:10.1071/CH11468

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Chemical Institute

The Nature of Hydrogen Bonding Involving the Siloxane Group

Simon Grabowsky ^A ^B ^D, Jens Beckmann ^A ^C and Peter Luger ^A

^A Freie Universität Berlin, Institut für Chemie und Biochemie/Anorganische Chemie, 14195 Berlin, Germany.
^B Current address: The University of Western Australia, School of Chemistry and Biochemistry, M313, Crawley WA 6009, Australia.
^C Current address: Universität Bremen, Institut für Anorganische und Physikalische Chemie, 28359 Bremen, Germany.
^D Corresponding author. Email: simon.grabowsky@uwa.edu.au

Australian Journal of Chemistry 65(7) 785-795 http://dx.doi.org/10.1071/CH11468
Submitted: 9 December 2011 Accepted: 6 February 2012 Published: 27 April 2012





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Abstract

Variation of the Si–O–Si angle in siloxane compounds is a way to tune their basicity from highly hydrophobic systems at linear geometry to hydrophilic systems at small angles. This has great potential in the design of new siloxane materials with properties distinct from those of known silicones. We investigate hydrogen bonds with the siloxane linkage as an acceptor in a large range of Si–O–Si angles for the two hydrogen-bonded complexes disiloxane⋯silanol [(H₃Si)₂O⋯HOSiH₃] and disiloxane⋯water [(H₃Si)₂O⋯HOH] with free disiloxane [H₃SiOSiH₃] as reference in a quantum-mechanical ab-initio study. Geometry, electron density, and the electron localizability indicator provide several complementary indicators of hydrogen bonding which show how Si–O–Si angle variation affects the nature and strength of these unusual hydrogen bonds.

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