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Unexpected Chemistry of Molecular Precursors to Boron Arsenide Materials
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DOI：10.1002/asia.70688.png)
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Abstract
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Simple arsine-boranes were explored as precursors to the semiconductor ceramic cubic boron arsenide (BAs). In preparing Ph2AsHBH3, spontaneous hydrogen loss was observed to give cyclo-arsine boranes, (Ph2AsBH2)n, and other products. At low temperature, Ph2AsHBH3 could be isolated and observed to engage in spontaneous hydrogen to form (Ph2AsBH2)n rings. These rings exhibit dynamic behavior through varying ratios of n = 3 or 4, but n = 5 could be observed and promoted under nonequilibrium conditions. Interestingly, the arsine substrate appears catalyze the decomposition of THF-borane, and simple boranes are catalysts for the dehydrocoupling of Ph2AsH. However, the most chemically odd observation was the relative lability of As-C bonds under mild conditions. While (Ph2AsBH2)n and Ph3AsBH3 are competent substrates for the formation of BAs products under pyrolysis conditions, particularly in air, ceramic yields suffer from from factors including volatility of the substrate under pyrolysis conditions and competitive arsenic oxidation occurred unpredictably. Arsenic chemistry aside, this overall strategy is valid for the production of bulk BAs substrates, though further substrate development is needed.
Keywords:
arsine borane
arsinoborane
ceramic precursor
dehydrocoupling
inorganic ring
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