Unusually high stability of B₁₂(BO)₁₂ ^2− achieved by boronyl ligand manipulation: Theoretical investigation

다국어 초록 (Multilingual Abstract)

<P><B>Abstract</B></P> <P>Density functional theory calculations of dodecaboronyldodecaborate (B<SUB>12</SUB>(BO)<SUB>12</SUB> <SUP>2−</SUP>) were performed to examine its electronic properties. Formation of this dianion with unusually high stability was accomplished by substituting boronyl (BO) for H in a typical dianion, B<SUB>12</SUB>H<SUB>12</SUB> <SUP>2−</SUP>. The binding energy of the second electron of the B<SUB>12</SUB>(BO)<SUB>12</SUB> <SUP>2−</SUP> dianion was 5.89 eV (PBE0/def2-TZVP) and 5.96 eV (MN12-SX/def2-TZVP); this represents its stability and is the largest value reported to date. We clarify that the high stability of B<SUB>12</SUB>(BO)<SUB>12</SUB> <SUP>2−</SUP> originates from the weak π orbital interaction character of the BO ligand. All calculated results clearly indicate the deficient π orbital interaction ability of BO.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The electronic properties of B<SUB>12</SUB>(BO)<SUB>12</SUB> <SUP>m</SUP> (m = 0, −1, and −2) are investigated. </LI> <LI> The high stability of B<SUB>12</SUB>(BO)<SUB>12</SUB> <SUP>2−</SUP> is achieved by ligand substitution. </LI> <LI> The π interaction of the BO ligand is weaker than that of CN ligand. </LI> <LI> B<SUB>12</SUB>(BO)<SUB>12</SUB> <SUP>2−</SUP> has the largest binding energy of the second electron. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>