15916-96-8Relevant academic research and scientific papers
Synthesis, spectral characterization and crystal structures of organophosphonic diamides: Pyramidal nitrogen centers and hydrogen bonding in [PhP(O)(NHtBu)2], [PhP(O)(NHDipp)2] (Dipp = 2,6-iPr2C6H3) and [tBuP(O)(NHiPr)2]
Murugavel, Ramaswamy,Pothiraja, Ramasamy
, p. 968 - 974 (2007/10/03)
Organophosphonic diamides of general formula [R1P(O)(NHR2)2] (1-8; R1 = Ph, Cy or tBu and R2 = Cy, iPr, tBu or Dipp) have been prepared by the addition of P,P′-dichloro(alkyl/aryl)phosphine oxide, R1P(O)Cl2, to a solution of primary amine in toluene. The synthesis of PhP(O)(NHtBu)2 (1) in high yield was achieved by slow oxidation of PhP(NHtBu)2 in air over several days. All new compounds have been characterized by elemental analysis and by IR, EI mass and NMR (1H and 31P) spectroscopy. The molecular structures of [PhP(O)(NHtBu)2] (1), [PhPO(NHDipp)2] (2) and [tBuP(O)(NHiPr)2] (7) have been determined by single crystal X-ray diffraction studies. The amido nitrogen atoms in 1, 2 and 7 show considerable deviation from the expected trigonal-planar geometry. The observed dihedral angles and the orientation of the nitrogen lone pair (l.p.) in these compounds point to the role of l.p.(N) → σ*(P-X) type negative hyperconjugative interactions in P-N multiple bonding. Compounds 1 and 7 form interesting polymeric structures in the solid state with the aid of N-H...O=P hydrogen bonding interactions while the presence of the very bulky Dipp substituent on nitrogen in 2 prevents the participation of the N-H protons in hydrogen bonding with phosphoryl oxygen atoms.
(N-lithioamino)diorganophosphanes and bis(N- lithioamino)organophosphanes: Synthesis and structures
Eichhorn, Bettina,Noeth, Heinrich,Seifert, Thomas
, p. 2355 - 2368 (2007/10/03)
Butyllithium (nBuLi) deprotonates Ph2P-NHtBu in ether to give (Ph2P- NLitBu)2 · OEt2. There is no Li ··· P interaction in this molecule. Three compounds of the type R'P(NLiR)2 have been obtained by li
LES PHOSPHORANES MONOCYCLIQUES A LIAISON PH DANS LES REACTIONS DE REDISTRIBUTION DE LIGANDS DES COMPOSES DU PHOSPHORE TRICOORDONNE
Tangour, B.,Malavaud, C.,Boisdon, M. T.,Barrans, J.
, p. 189 - 196 (2007/10/02)
The oxidative addition of alcohols and amines with 2-alkyl, 2-aryl, 1,3,2-dioxa, oxaza or diazaphospholanes, leads to a ring opening reaction and ligands exchange around the phosphorus atom by alcoholysis or aminolysis of P-O or P-N bonds.In nearly all cases, monocyclic phosphoranes with P-H bond have been detected in an intermediate step during the exchange of one tricoordinate form to another one.At last we have discussed the phorpholanyl ring stability. - Key words: 1,3,2-Dioxaphospholanes; 1,3,2-oxaza-phospholanes; 1,3,2-diazaphospholanes; Monocyclic phosphoranes with P-M bonds; phosphoranyl ring stability.
