KINETICS OF THE DECOMPOSITION OF BH3PF3 AND RELATED COMPOUNDS; A REVISED ESTIMATE OF THE DISSOCIATION ENERGY OF DIBORANE.
Abstract
Very sensitive IR procedures were used to show that the compounds BH3PF3, BH3.CF3PF2, and BH3.(CF3)2PF all decompose to B2H6 and free phosphine-ligand by the same mechanism as found earlier for BH3CO, namely, the dissociation of BH3L to BH3 and free ligand L, followed by action of BH3 to displace L from BH3L. The same rate law applies also to the far more complicated case of B4H8PF3. Extrapolation of early-stage rate data for BH3PF3 to zero time gave first-order rate constants for the initial dissociation at three temperatures. These results, taken with the over-all equilibria, led to D(BH3-BH3) = 35.1 kcal., consistent with but more precise than earlier estimates. The only systematic error here would arise from the reasonable assumption that delta H = O for activation of the reverse of the initial dissociation. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Oct 25, 1965
- Accession Number
- AD0473727
Entities
People
- Anton B. Burg
- Yuan C. Fu
Organizations
- University of Southern California