Dative versus electron-sharing bonding in N-imides and phosphane imides R 3 ENX and relative energies of the R 2 EN(X)R isomers (E = N, P; R = H, Cl, Me, Ph; X = H, F, Cl) *

Tao Yang, Diego M. Andrada, Gernot Frenking

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

Quantum chemical calculations using density functional theory BP86 and M06-2X functionals in conjunction with def2-TZVPP basis sets have been carried out on the title molecules. The calculation results reveal that the N-imides R 3 NNX are always clearly higher in energy than the imine isomers R 2 NN(X)R. In the case of phosphane imides R 3 PNX and the isomers R 2 PN(X)R, the substituent R plays a critical role in determining their relative stabilities. When R is hydrogen or phenyl group, R 3 PNX are always higher in energy than R 2 PN(X)R but the former are more stable than the latter when R = Cl. Interestingly, the Me 3 PNX and Me 2 PN(X)Me are quite close in energy. The energy decomposition analysis suggests that the P–N bond in the phosphane imides R 3 PNX (R = H, Cl, Me, Ph; X = H, F, Cl) should be described in terms of an electron-sharing single bond between two charged fragments R 3 P + -NX that is supported by (R 3 P) + ←(NX) π-backdonation. The π-bond contributes 14–21% of the total orbital interactions while the σ-bond provides 60–68% of ΔE orb .

Original languageEnglish
Pages (from-to)1306-1314
Number of pages9
JournalMolecular Physics
Volume117
Issue number9-12
DOIs
StatePublished - 18 Jun 2019

Keywords

  • Chemical bond
  • DFT
  • N-imides
  • energy decomposition analysis
  • phosphane imides

Fingerprint

Dive into the research topics of 'Dative versus electron-sharing bonding in N-imides and phosphane imides R 3 ENX and relative energies of the R 2 EN(X)R isomers (E = N, P; R = H, Cl, Me, Ph; X = H, F, Cl) *'. Together they form a unique fingerprint.

Cite this