Chemistry and Structures of Hexakis(halogenomethyl)‐, Hexakis(azidomethyl)‐, and Hexakis(nitratomethyl)disiloxanes
Abstract
An investigation of the structures and chemistry of substituted hexamethyl disiloxanes ((XCH2)3Si)2O; X=F, Cl, Br, I, N3, and ONO2) is reported. New synthetic routes to the precursor hexakis(chloromethyl)disiloxane are presented. The products with X=Cl, Br, I, and N3 were characterized by NMR, IR, and Raman spectroscopy. In addition, the single‐crystal structures of the products with X=Cl, Br, and I are discussed in detail. The compounds with X=F and ONO2 were not obtained in their pure form; instead investigations of the decomposition products revealed their conversion into intermediates. Theoretical calculations of the gas‐phase structures at the B3LYP/cc‐pVDZ, B3LYP/3‐21G, MP2/6‐31G*, and MP2/3‐21G levels of theory are used to explain the chemical and physical behavior of the compounds with X=Cl, Br, I, N3, and ONO2. A new decomposition pathway of hexakis(nitratomethyl)disiloxane is presented and is used to explain their remarkable instability. The energetic properties and values of the nitrate and azide derivatives were calculated at the CBS‐4M level of theory by using the improved EXPLO5 computer code version 6.01.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- May 31, 2013
- Source ID
- 10.1002/chem.201300226
Entities
People
- Anian Nieder
- Burkhard Krumm
- Camilla Evangelisti
- Christian Schütz
- Julia Nafe
- Laura Ascherl
- Matthias Trunk
- Muhamed Sućeska
- Sebastian Rest
- Thomas M. Klapötke
Organizations
- Australian RL Commission
- Ludwig-Maximilians-Universität München
- Office of Naval Research
- United States Army Armament Research, Development and Engineering Center
- United States Army Research Laboratory