The effects of metal-based additives in a wide range of elements doping into ammonia borane (AB) were systematically investigated. Pure transition metals in period 4 and total of 17 metal chlorides were selected as additives and ball-milled with AB. Metal chloride additives were effective to decrease H 2 desorption temperature and the amounts of byproduct gas emissions of AB, whereas pure transition metals did not show any ability because they did not work as Lewis acids. The strong correlation between H 2 desorption temperature and the Pauling electronegativity of metal (χ p ) was observed. M n + of MCl n would work as Lewis acid to initiate the AB dehydrocoupling reaction. The amount of NH 3 emission was correlated with the ionic radius of M, suggesting MCl n · m NH 3 complexes be formed in this system. AB–CuCl 2 and AB–AgCl mixtures showed the similar H 2 desorption processes. The Cl-containing intermediate phase would destabilize AB during reaction.
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Nakagawa et al. (2016) studied this question.
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