MECHANISMS OF ISOTOPIC EXCHANGES IN THE BORON HYDRIDES. Technical Note No. 11
Technical Report
·
OSTI ID:4242556
The exchange of deuterium and B/sup 10/ between diborane and several of the more common boron hydrides was studied with the expectation that a knowledge of the exchange mechanism will give a better insight into the nature of the intermediate fragments that play an important role in the chemtstry of these compounds. Evidence has been accumulated for at least three mechanisms by which isotopic exchange proceeds in the boron hydrides. In the diborane self-exchange the reaction appears to involve borane as an entity and the ratio of deuterium rate to boron rate is three. In the B/sub 2/D/sub 6/-B/sub 5/ H/sub 9/ exchange the rate-determining step is the reaction of borane with the terminal hydrogens of pentaborane. The bridge hydrogens are not involved at all. A similar situation exists in the diborane-decaborane exchange. In the B/sub 2/D/sub 6/-B/ sub 5/H/sub 11/ reaction the fraction-order kinetics indicate that the B/sub 5/H/ sub 11/ is fragmenting. All of the borons and all of the hydrogens in both molecules are participating in the exchange. Only one rate of exchange has been observed but there is experimental evidence that exchange can proceed by an intramolecular mechanism. In the case of the B/sub 2/D/sub 6/-B/sub 4/H/sub 10/ reaction one has at least two mechanisms of isotopic exchange and evidence has been obtained for an exchange that proceeds by an intramolecular mechanism. The intramolecular process is an indication of the lability of the hydrogens and the borons in some of the less stable boron hydrides. (auth)
- Research Organization:
- Johns Hopkins Univ., Baltimore
- NSA Number:
- NSA-13-017774
- OSTI ID:
- 4242556
- Report Number(s):
- AFOSR-TN-59-613; AD-217400
- Country of Publication:
- United States
- Language:
- English
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