Unraveling the Crucial Role of Metal-Free Catalysis
in Borazine and Polyborazylene Formation in Transition-Metal-Catalyzed
Ammonia–Borane Dehydrogenation
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Abstract
Though
the recent scientific literature is rife with experimental
and theoretical studies on transition-metal (TM)-catalyzed dehydrogenation
of ammonia–borane (NH<sub>3</sub>·BH<sub>3</sub>) due
to its relevance in chemical hydrogen storage, the mechanistic knowledge
is mostly restricted to the formation of aminoborane (NH<sub>2</sub>BH<sub>2</sub>) after 1 equiv of H<sub>2</sub> removal from NH<sub>3</sub>·BH<sub>3</sub>. Unfortunately, the chemistry behind
the formation of borazine and polyborazylene, which happens only after
more than 1 equiv of H<sub>2</sub> is released from ammonia–borane
in these TM-catalyzed homogeneous reactions, largely remains unknown.
In this work we use density functional theory to unravel the curious
function of “free NH<sub>2</sub>BH<sub>2</sub>”. Initially,
free NH<sub>2</sub>BH<sub>2</sub> molecules form oligomers such as
cyclotriborazane and <i>B</i>-(cyclodiborazanyl)aminoborohydride.
We show that, through a web of concerted proton and hydride transfer
based dehydrogenations of oligomeric intermediates, cycloaddition
reactions, and hydroboration steps facilitated by NH<sub>2</sub>BH<sub>2</sub>, the development of the polyborazylene framework occurs.
The rate-determining free energy barrier for the formation of a polyborazylene
template is predicted to be 25.7 kcal/mol at the M05-2X(SMD)/6-31++G(d,p)//M05-2X/6-31++G(d,p)
level of theory. The dehydrogenation of BN oligomeric intermediates
by NH<sub>2</sub>BH<sub>2</sub> yields NH<sub>3</sub>·BH<sub>3</sub>, suggesting for certain catalytic systems that the role of
the TM catalyst is limited to the dehydrogenation of NH<sub>3</sub>·BH<sub>3</sub> to maintain optimal amounts of free NH<sub>2</sub>BH<sub>2</sub> in the reaction medium to enable polyborazylene formation.
TM catalysts that fail to produce borazine and polyborazylene falter
because they rapidly consume NH<sub>2</sub>BH<sub>2</sub> in TM-catalyzed
polyaminoborane formation, thus preventing the chain of events triggered
by NH<sub>2</sub>BH<sub>2</sub>