New structural motif of 18 valence electron molecules with a planar tetracoordinate heavier group 14 center: Unique stabilization effect of a π‐type skeleton. Issue 22 (6th July 2017)

• Record Type: Journal Article
• Authors: Yu, Shuang; Ding, Yi‐Hong
• Is Part Of: International journal of quantum chemistry. Volume 117:Issue 22(2017)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2017-07-06
• Subjects: computation -- global minima -- heavier group 14 elements -- planar tetracoordinate -- π‐type skeleton; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.25436
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: Proposing new valence electron counting rules and new structural motifs are both very important in chemistry. In this work, we unexpectedly found that by introducing a π‐type skeleton YCCY (Y = Al/Ga/In/Tl), a total of sixteen novel planar tetracoordinate heavier group 14 species, that is, ptM (M = Si/Ge/Sn/Pb) in neutral, can be designed as global minima. The underlying bonding situation contrasts sharply both with the well‐known 18ve‐ptC and the limited 18ve‐ptM, for which there is little multiple bonding character within the skeleton. The fact that each YCCY (Y = Al/Ga/In/Tl) can stabilize all heavier group 14 atoms in a planar tetracoordinate fashion strongly demonstrates the universality of such a π‐type skeleton. The present work firmly demonstrates that introducing the π‐type ligand skeleton can effectively enrich the planar tetracoordinate chemistry with the heavier group atoms. Abstract : First‐principles calculations predict the stability of sixteen new planar tetracoordinate Group 14 molecules C2 Y2 M (Y = Al/Ga/In/T; M = Si/Ge/Sn/Pb), with π‐type skeleton. The underlying bonding situation contrasts sharply both with the well‐known 18ve‐ptC and the limited 18ve‐ptM rules, which expect note to little multiple bonding character within the skeleton. Because the YCCY structure is found to stabilize all group 14 atoms in a planar tetracoordinate fashion, the universality of such π‐type skeleton is suggested.