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Donor−Acceptor Complexes of Borazines

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journal contribution
posted on 15.11.2010, 00:00 authored by Anna S. Lisovenko, Alexey Y. Timoshkin
Donor−acceptor complexes of borazine (BZ) and its substituted derivatives with Lewis acids (A = MCl3, MBr3; M = B, Al, Ga) and Lewis bases (D = NH3, Py) have been theoretically studied at the B3LYP/TZVP level of theory. The calculations showed that complexes with Lewis bases only are unstable with respect to dissociation into their components, while complexes with Lewis acids only (such as aluminum and gallium trihalides) are stable. It was shown that formation of ternary D→BZ→A complexes may be achieved by subsequent introduction of the Lewis acid (acceptor A) and the Lewis base (donor D) to borazine. The nature of substituents in the borazine ring, their number, and position were shown to have only minor influence on the stability of ternary D→BZ→A complexes due to the compensation effect. Much weaker acceptor properties of borazine are explained in terms of large endothermic pyramidalization energy of the boron center in the borazine ring. In contrast to borazine, binary complexes of the isoelectronic benzene were predicted to be weakly bound even in the case of very strong Lewis acids; ternary DA complexes of benzene were predicted to be unbound. The donor−acceptor complex formation was predicted to significantly reduce both the endothermicity (by 70−95 kJ mol−1) and the activation energy (by 40−70 kJ mol−1) for the borazine hydrogenation. Thus, activation of the borazine ring by Lewis acids may be a facile way for the hydrogenation of borazines and polyborazines.