Theoretical Investigation of Promising Molecules for Obtaining Complexes with Planar Tetracoordinate Carbon

Congjie Zhang; Dongxia Ma; Shaoni Yang; Jinxia Liang

doi:10.1021/acsomega.6b00170

Theoretical Investigation of Promising Molecules for Obtaining Complexes with Planar Tetracoordinate Carbon

ACS Omega. 2016 Oct 19;1(4):620-625. doi: 10.1021/acsomega.6b00170. eCollection 2016 Oct 31.

Authors

Congjie Zhang¹, Dongxia Ma¹, Shaoni Yang¹, Jinxia Liang²

Affiliations

¹ Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Changan South Road 199, Xi'an 710062, P. R. China.
² Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Education University, 115 Gaoxin Road, Wudang District, Guiyang 550018, P. R. China.

Abstract

We have theoretically investigated the stability, chemical bonding, and coordination ability of the 2-Me-2-borabicyclo[1.1.0]but-1(3)-ene (2-Me-2BB) molecule using density functional theory and ab initio molecular dynamics (AIMD) simulations. Calculated results indicated that 2-Me-2BB is both thermodynamically and kinetically stable. The C=C bonds in 2-Me-2BB contain a π bond and a charge shift (CS) bond, different from those in 1-Me-borirene and cyclopropylene. Moreover, 2-Me-2BB can be a σ donor, leading to the formation of TM(2-Me-2BB)L _n complexes containing planar tetracoordinate carbon (ptC) with transition metals (TM = Sc-Cu), in which the lone electron pair of 2-Me-2BB results from its ionic resonance form. The lengths and Wiberg bond indices of the TM-ptC bond in TM(2-Me-2BB)L _n (TM = Sc-Cu) reveal that 2-Me-2BB can be a ligand similar to N-heterocyclic carbene. Therefore, 2-Me-2BB and its derivatives are promising molecules to obtain complexes with ptC. The natural charges on TM atoms in TM(2-Me-2BB)L _n (TM = Sc-Cu) complexes range from -0.97 to 1.54e, indicating that such complexes with ptC might have potential applications in catalytic chemistry.