From Saturated BN Compounds to Isoelectronic BN/CC Counterparts: An Insight from Computational Perspective

In the present study, the inorganic analogues of alkanes as well as their isoelectronic BN/CC counterparts that bridge the gap between organic and inorganic chemistry are comparatively studied on the grounds of static DFT and Car-Parrinello molecular dynamics simulations. The BN/CC butanes CH3 CH2 BH2 NH3 , BH3 CH2 NH2 CH3 , and NH3 CH2 BH2 CH3 were considered and compared with their isoelectronic counterparts NH3 BH2 NH2 BH3 and CH3 CH2 CH2 CH3 . In addition, systematical replacement of the NH2 BH2 fragment by the isoelectronic CH2 CH2 moiety is studied in the molecules H3 N(NH2 BH2 )3-m (CH2 CH2 )m BH3 (for m=0, 1, 2, or 3) and H3 N(NH2 BH2 )2-m (CH2 CH2 )m BH3 (for m=0, 1, or 2). The DFT and Car-Parrinello simulations show that the isosteres of the BN/CC butanes CH3 CH2 BH2 NH3 , BH3 CH2 NH2 CH3 , and NH3 CH2 BH2 CH3 and of larger oligomers of the type (BN)k (CC)l where k≥l are stable compounds. The BN/CC butane H3 NCH2 CH2 BH3 spontaneously produces molecular hydrogen at room temperature. The reaction, prompted by very strong dihydrogen bonding NH⋅⋅⋅HB, undergoes through the neutral, hypervalent, pentacoordinated boron dihydrogen complex RBH2 (H2 ) [R=(CH2 CH2 )n NH2 ]. The calculations suggest that such intermediate and the other BN/CC butanes CH3 CH2 BH2 NH3 , BH3 CH2 NH2 CH3 , and NH3 CH2 BH2 CH3 as well as larger BN/CC oligomers are viable experimentally. A simple recipe for the synthesis of CH3 CH2 BH2 NH3 is proposed. The strength of the dihydrogen bonding appeared to be crucial for the overall stability of the saturated BN/CC derivatives.