Accession Number : AD0473727


Title :   KINETICS OF THE DECOMPOSITION OF BH3PF3 AND RELATED COMPOUNDS; A REVISED ESTIMATE OF THE DISSOCIATION ENERGY OF DIBORANE.


Descriptive Note : Technical rept.,


Corporate Author : UNIVERSITY OF SOUTHERN CALIFORNIA LOS ANGELES DEPT OF CHEMISTRY


Personal Author(s) : Burg ,Anton B ; Fu,Yuan C


Report Date : 25 Oct 1965


Pagination or Media Count : 16


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)


Descriptors :   *BORON COMPOUNDS , *DIBORANES , *DECOMPOSITION , REACTION KINETICS , DISSOCIATION , BORANES , PHOSPHORUS COMPOUNDS , PHOSPHINE , FLUORIDES , INFRARED SPECTRA , THERMOCHEMISTRY , HEAT OF ACTIVATION , ORGANOBORANES , COMPLEX COMPOUNDS


Distribution Statement : APPROVED FOR PUBLIC RELEASE