Silylene rearrangements in the reactions of recoiling silicon atoms with trimethylsilane

Journal Article · Wed Mar 10 04:00:00 EST 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00369a047· OSTI ID:5658327

Mo, S H; Holten, III, J D; Konieczny, S; Ma, E C; Gaspar, P P

The exploration of atom-molecule reactions above their threshold energies is a major task of hot-atom chemists, and where comparisons have been made, the recoil reactions differ significantly from their thermal counterparts. This is the case for the reactions of recoiling silicon atoms with trimethylsilane. Free atoms were produced by the /sup 31/P(n,p)/sup 31/Si nuclear transformation induced in gaseous mixtures of phosphine and trimethlysilane by cyclotron-produced fast neutrons. The products detected are given in order of increasing vapor-chromatographic retention times. n + PH/sub 3/ ..-->.. p + /sup 31/Si + 3H; /sup 31/Si + HSiMe/sub 3/ ..-->../PH/sub 3/ /sup 31/SiH/sub 4/ (2%) + H/sub 3/ /sup 31/SiMe (0.5%) + unknown (0.1%) + H/sub 3/ /sup 31/SiSiMe/sub 3/ (36%) + MeH/sub 2/ /sup 31/SiSiMe/sub 3/ (10%) + unknown (5%) + Me/sub 3/Si /sup 31/SiH/sub 2/SiMe/sub 3/ (5%) + A (3%) 1. This communication attributes the formation of products 1 and A to silylene intermediates. A recently discovered rearrangement of silylenes has led to the identification of A and forms the basis for a mechanism that follows a /sup 31/Si atom from its initial reactive encounter with a HSiMe/sub 3/ molecule to 1 and A. (DP)

• Research Organization: Washington Univ., Saint Louis, MO
• OSTI ID: 5658327
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:5; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400701* -- Radiochemistry & Nuclear Chemistry-- Hot-Atom Chemistry
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
CHEMISTRY
EVEN-ODD NUCLEI
HOT ATOM CHEMISTRY
HOURS LIVING RADIOISOTOPES
HYDRIDES
HYDROGEN COMPOUNDS
ISOTOPES
LIGHT NUCLEI
NUCLEI
RADIOCHEMISTRY
RADIOISOTOPES
REACTION INTERMEDIATES
RECOILS
SILANES
SILICON 31
SILICON COMPOUNDS
SILICON ISOTOPES