New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of Ph₂P(X)NH(C₆H₃Prⁱ₂-2,6) (X = O, S) and (OPPh₂)(O₂SMe)N(C₆H₃Prⁱ₂-2,6)

Abstract

The new organophosphorus proligand (OPPh₂)(O₂SMe)NR (R = C₆H₃Prⁱ ₂–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph₂P(O)NR] with MeSO₂Cl in a 1:1 molar ratio. The precursor Ph₂P(O)NHR (1), as well as its thio analogue Ph₂P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O˭P(C)₂–N–S(C)(˭O)₂ skeleton.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

Keywords:

• Molecular structure
• NMR spectroscopy
• organophosphorus ligands

Acknowledgments

This work was supported by the National University Research Council of Romania (CNCSIS grant: A-1456/2008). S.I. is grateful for financial support in the form of a Scientific and Technical Research Council of Turkey (TUBITAK)–NATO B2 fellowship.