The Effects of Low Energy Irradiation on Organometallics. Organometal Halides of Group IVA

F E Brinckman; Gerald F Kokoszka; Norman K Adams Jr

doi:10.6028/jres.073A.017

The Effects of Low Energy Irradiation on Organometallics. Organometal Halides of Group IVA

J Res Natl Bur Stand A Phys Chem. 1969 Mar-Apr;73A(2):201-206. doi: 10.6028/jres.073A.017.

Authors

F E Brinckman¹, Gerald F Kokoszka¹, Norman K Adams Jr¹

Affiliation

¹ Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234.

Abstract

A group of selected group IVA halides of the type (CH₃) _n MCl_4-n , where n = 0, 1, 3 and M = Si, Ge, Sn have been subjected to low-energy irradiation (254 and 370 nm) in the condensed phase at - 196°C. This survey also examined related compounds including HSiCl₃, CH₂ClSiCl₃, CH₃SiF₃, CH₃SiHCl₂ as well as cocondensed mixtures. It is demonstrated by EPR spectroscopy that these conditions suffice to cleave M-C bonds. By following spectral changes during or following irradiation, as a function of time, it is demonstrated that both primary and secondary reactions occur. Some general features of the spectra are discussed and certain conclusions are projected to additional studies on low temperature reactions in 1:1 cocondensed mixtures of organometal halides. Some preliminary supporting evidence from mass spectrometric observations is discussed.

Keywords: EPR; free radicals; germanium; irradiation; low-temperature reaction; organometallic compounds; silicon; tin.