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(NHC)3→B+B-←(CO)2: a allotrope of boron in ionic form stabilized by Lewis base
  • xiaoyong yang
xiaoyong yang
QiLu University of Technology (Shandong Academy of Science)

Corresponding Author:zidu113@qlu.edu.cn

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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.