Reactions of recoiling silicon atoms with phosphine-diene mixtures and the question of silylene intermediates

Journal Article · Wed Oct 11 04:00:00 EDT 1978 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00489a012· OSTI ID:6509024

Hwang, R J; Gaspar, P P

Reactions of silicon atoms recoiling from the /sup 31/P(n,p)/sup 31/Si nuclear transformation in phosphine--butadiene mixtures yield (/sup 31/Si)-1-silacyclopent-3-ene, also obtained in 46% yield from reaction of thermally generated SiH/sub 2/ with butadiene, and a product believed to be (/sup 31/Si)-1-silacyclopenta-2,4-diene. The variation of product yields with the composition of PH/sub 3/--SiH/sub 4/--C/sub 4/H/sub 6/ recoil reaction mixtures casts doubt on the participation of ground-state singlet silylene /sup 31/SiH/sub 2/ as a reactive intermediate, as does the failure to detect any of the thermal adduct of silylene to cyclopentadiene 1-silacyclohexa-2,4-diene from the reactions of /sup 31/Si in PH/sub 3/--SiH/sub 4/-c-C/sub 5/H/sub 6/ mixtures. Alternative mechanisms are considered. Thermally generated Mc/sub 2/Si does not abstract hydrogen atoms from Me/sub 3/SiH, but inserts into the Si--H bond. 6 figures; 3 tables.

• Research Organization: Washington Univ., St. Louis, MO
• OSTI ID: 6509024
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 100:21; 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
ALKENES
ATOMS
BARYONS
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
BUTADIENE
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
COMPARATIVE EVALUATIONS
CYCLOALKENES
CYCLOPENTADIENE
DECOMPOSITION
DIENES
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
FAST NEUTRONS
FERMIONS
HADRONS
HOT ATOM CHEMISTRY
HOURS LIVING RADIOISOTOPES
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
IRRADIATION
ISOTOPES
KINETICS
LIGHT NUCLEI
LOW PRESSURE
MEDIUM PRESSURE
NEUTRONS
NUCLEI
NUCLEONS
ORGANIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
POLYENES
PRESSURE DEPENDENCE
QUANTITY RATIO
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOCHEMISTRY
RADIOISOTOPES
RADIOLYSIS
REACTION INTERMEDIATES
REACTION KINETICS
RECOILS
SILANES
SILICON 31
SILICON COMPOUNDS
SILICON ISOTOPES
SUBSTRATES
YIELDS