PHOTOCHEMICAL INSERTION REACTION OF HG IN SIH4 SID4 IN LOW-TEMPERATURE N-2, AR, AND KR MATRICES - FORMATION OF RADICALS IN KR/

The products of the insertion reaction of Hg(P-3(1)) in the SiH (SiD) bond of h- or d-silane in nitrogen and rare gas matrixes are observed by FTIR spectroscopy. This study has shown that the reaction takes pla ce without activation energy. Disilane molecules are formed from the d imers of parent molecules close to mercury or from the complexes of th e insertion products with the parent molecules. In this last case a we ak isotopic effect shows that the reaction probably takes place throug h a small barrier. In the krypton matrix the formation of SiH2 and SiH radicals is observed by a mercury-sensitized two-photon excitation. T he SiH3 radical is produced upon annealing. A mixed CH4/SiH4 experimen t gives the ratio of the insertion rates in these two molecules.