10-Valence-Electron C≡O and the 14-VE C≡Pt: Two Triple-Bonded Isoelectronic Families Differing by a dδ⁴ Ring

Abstract

10-VE A≡A′ Diatomics, such as N≡N, C≡O, etc., have a strong σ 2 π 4 triple bond plus a lone pair at each end. In our studies on 14-VE A≡B systems, such as C≡Pt, we find a similar bonding system plus a (5 d δ) 4 ring. Here, the A atom belongs to groups 13–17 and the B atom to groups 7–11. Also the BB′ combinations, triatomics, such as PtCO or DsCO or uranyl, and longer chains, such as AuCN and [NC-Au-CN] − , are discussed. The δ ring directly contributes to nuclear quadrupole coupling constants, and DFT calculations using the BH and H or mPW1K functionals reproduce the experimental trends of the NQCC.