23777-80-2Relevant articles and documents
Kinetic studies of reactions of hexaborane(10) with other binary boranes in the gas phase
Attwood, Martin D.,Greatrex, Robert,Greenwood, Norman N.,Potter, Christopher D.
, p. 144 - 152 (2007/10/03)
Cothermolysis reactions of B6H10 with the binary boranes B2H6, B4H10, B5H9, and B5H11 have been studied by a quantitative mass-spectrometric technique to gain insight into the role of B6H10 in borane interconversion reactions. Except in the B6H10-B5H9 system the initial rate of consumption of B6H10 was found to be considerably more rapid than in the thermolysis of B6H10 alone, indicating that interactions were occuring. Detailed kinetic studies of the B6H10-B2H6 and B6H10-B4H10 reactions showed that the rate of consumption of B6H10 was governed in each case by the rate-determining step in the decomposition of the co-reactant, the orders being 3/2 with respect to B2H6 and 1 with respect to B4H10; a considerable increase in the conversion of B6H10 to B10H14 at the expense of polymeric solids was also observed. Added hydrogen was found to have very little effect on the reaction rates and product distributions in the cothermolysis reactions, in marked contrast to its effect on the reactions of B2H6 and B4H10 alone. The kinetic results are entirely consistent with earlier suggestion, based on qualitative observations, that the reactive intermediates {B3H7} and {B4H8} are scavenged by reactions with B6H10, and suggest strongly that this borane, unlike B6H12, plays a pivotal role in the build-up to B10H14 and other higher boranes.
KINETICS AND MECHANISM OF THE THERMOLYSIS AND PHOTOLYSIS OF BINARY BORANES.
Greenwood,Greatrex
, p. 857 - 868 (2008/10/08)
The mechanisms by which gaseous boron hydrides so readily interconvert and build up into larger clusters has excited considerable academic and industrial interest for several decades. This paper describes recent progress that has been made in unravelling this complex series of interconversion reactions. Initial reaction rates have been studied mass spectrometrically to obtain rate equations, orders of reaction and energies of activation. Detailed and continuous product analysis for H//2 and all the volatile boranes formed, coupled with a study of cothermolysis reactions of selected pairs of boranes gives further insight into the processes occurring. Crucial aspects of the thermolysis of B//2H// 6, B//4H//1//0, B//5H//1//1, and B//6H//1//0 are discussed, as are the effects of the added H//2 and the cothermolysis of B//6H//1//0 with alkenes. The final section presents data on the UV absorption spectra and photolytic stability of eight volatile boranes and the reaction kinetics of B//6H//1//0 photolysis.
