Covalency and Ionicity Do Not Oppose Each Other-Relationship Between Si-O Bond Character and Basicity of Siloxanes

Chemistry : a European Journal
Malte FugelSimon Grabowsky

Abstract

Covalency and ionicity are orthogonal rather than antipodal concepts. We demonstrate for the case of siloxane systems [R3 Si-(O-SiR2 )n -O-SiR3 ] that both covalency and ionicity of the Si-O bonds impact on the basicity of the Si-O-Si linkage. The relationship between the siloxane basicity and the Si-O bond character has been under debate since previous studies have presented conflicting explanations. It has been shown with natural bond orbital methods that increased hyperconjugative interactions of LP(O)→σ*(Si-R) type, that is, increased orbital overlap and hence covalency, are responsible for the low siloxane basicity at large Si-O-Si angles. On the other hand, increased ionicity towards larger Si-O-Si angles has been revealed with real-space bonding indicators. To resolve this ostensible contradiction, we perform a complementary bonding analysis, which combines orbital-space, real-space, and bond-index considerations. We analyze the isolated disiloxane molecule H3 SiOSiH3 with varying Si-O-Si angles, and n-membered cyclic siloxane systems Si2 H4 O(CH2 )n-3 . All methods from quite different realms show that both covalent and ionic interactions increase simultaneously towards larger Si-O-Si angles. In addition, we present hig...Continue Reading

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Citations

Oct 10, 2019·Chemistry : a European Journal·Fabian DankertCarsten von Hänisch
Oct 18, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Malte FugelSimon Grabowsky
Apr 22, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Maximilian JostCarsten von Hänisch
Aug 12, 2020·Chemistry : a European Journal·Radhika GuptaGilles Frison
Feb 17, 2021·Angewandte Chemie·Fabian DankertCarsten von Hänisch
May 12, 2021·The Journal of Physical Chemistry. a·Malte FugelSimon Grabowsky
Jun 25, 2021·Chemical Science·Florian KleemissSimon Grabowsky
Jul 10, 2021·Inorganic Chemistry·Moritz AchternboschCarsten Strohmann
Sep 12, 2020·The Journal of Physical Chemistry. a·Ionut-Tudor MoraruGabriela Nemes
Nov 12, 2021·Chemistry : a European Journal·Tobias GötzJonathan O Bauer
Jan 21, 2022·Chemical Communications : Chem Comm·Nicolò FontanaJonathan O Bauer

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