Structural Chemistry

, Volume 22, Issue 1, pp 201–210

Different orientations of C=O versus P=O in P(O)NHC(O) skeleton: the first study on an aliphatic diazaphosphorinane with a gauche orientation

  • Atekeh Tarahhomi
  • Mehrdad Pourayoubi
  • Arnold L. Rheingold
  • James A. Golen
Original Research

DOI: 10.1007/s11224-010-9682-y

Cite this article as:
Tarahhomi, A., Pourayoubi, M., Rheingold, A.L. et al. Struct Chem (2011) 22: 201. doi:10.1007/s11224-010-9682-y

Abstract

Different orientations of P(O) versus C(O) in P(O)NHC(O) skeleton have been discussed in two new phosphorus(V)-nitrogen compounds with formula XP(O)Y and XP(O)Z2 where X = NHC(O)C6H4(4-F) and Y = NHCH2C(CH3)2CH2NH (1), Z = NHC6H4(4-CH3) (2). Compound 1 is the first example of an aliphatic diazaphosphorinane with a gauche orientation which has been studied by X-ray crystallography; the P=O bond is in the equatorial position of the ring. Both compounds show nJ(F,C) and mJ(F,H) coupling constants (n = 1, 2, 3 and 4; m = 3 and 4) and 3J(P,C) > 2J(P,C). Quantum chemical calculations were performed with HF and Density Functional Theory (DFT) methods using 6−31+G(d,p) basis set. A tentative assignment of the observed vibrational bands for these molecules is discussed. Compound 1 shows a deshielded C atom of the carbonyl moiety (in 13C NMR spectrum) relative to that of 2, which is supported by IR spectroscopy in which the considerably lower C=O frequency is observed for 1. Comparing the X-ray crystallography and IR spectra of 1 and 2 shows that the acyclic compound 2, containing P=O and C=O bonds in an anti position, are involving in a stronger N–H···O=P hydrogen bond in crystal network. This leads to a weaker P=O and NC(O)NHP(O)–H bonds and stronger N···O interaction. The Namide–H is involved in an intramolecular N–H···O hydrogen bond.

Keywords

Phosphoric triamides NMR X-ray crystallography Hydrogen bonds Chemical calculation 

Supplementary material

11224_2010_9682_MOESM1_ESM.doc (952 kb)
Supplementary material 1 (DOC 952 kb)

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  • Atekeh Tarahhomi
    • 1
  • Mehrdad Pourayoubi
    • 1
  • Arnold L. Rheingold
    • 2
  • James A. Golen
    • 2
  1. 1.Department of ChemistryFerdowsi University of MashhadMashhadIran
  2. 2.Department of ChemistryUniversity of California, San DiegoLa JollaUSA