Abstract
In this paper, we divide allotropes into two categories, one is the
zero-oxidation state allotrope and the other is the ionic form
allotrope. So far, many main group complexes L→Mn←L( L,
Lewis base ligands; M, main group element) have been found, which can
be regarded as zero-oxidation state allotrope of the main group
elements stabilized by Lewis base ligands. However, few compounds
L→Mn+Mn-←L
containing ionic form allotropes of the main group elements have been
reported. This class of compounds
L→Mn+Mn-←L
is found only in s-block alkalide salts. In this work, we have
theoretically confirmed that this class of compound
L→Mn+Mn-←L
can be extended to P-block boron. Rigorous thermodynamic calculations
based on Born–Haber cycle confirm
that (NHC)3→B+ and
(CO)2→B-are a compatible pair of
positive and negative ions, which can form stable
[(NHC)3→B+][(CO)2→B-]
crystalline salt. More importantly, the bonding analysis of
(NHC)3→B+ and
(CO)2→B- based on frontier orbital
analysis and NBO show that (NHC)3→B+
and (CO)2→B- can be regarded as
positive monovalent boron B(1) and negative monovalent boron B(-1)
complexes stabilized by Lewis base, respectively. So
[(NHC)3→B+][(CO)2→B-]
crystalline salt can be viewed as“B+B-”ionic salts stabilized by Lewis
base ligands: an allotrope of boron in ionic form through asymmetric
coordination of Lewis base.