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)

The new organophosphorus proligand (OPPh2)(O2SMe)NR (R = C6H3Pri2-2,6) (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 center dot center dot center dot 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.