On the Reactivity of the Iminodiphosphane C₆H₄(o‐CN)N=PPh₂−PPh₂: Fragmentation Versus Isomerisation

Abstract

The reactivity of the iminodiphosphane C6H4(o‐CN)N=PPh2−PPh2, which contains an N=P−P unit, has been investigated. Reaction with small molecules, [viz. H2O/O2, H2O2, CH3OH, C6H4(o‐CN)NH2] and elemental sulfur result in cleavage of the P−P bond to give aminophosphane‐derivatised compounds. The products from these reactions have been characterized spectroscopically, including two by single‐crystal X‐ray diffraction. The reactivity of the iminodiphosphane towards the transition metal complexes [M(cod)Cl2] (M = Pd or Pt) has also been investigated. In the reactions, the iminodiphosphane rearranges to form the more common diphosphonylamine (P−N−P) unit which chelates to the metal centres. Three different compounds were isolated from these reactions and they have all been fully characterised by spectroscopy and single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Crystal structure of N-diphenylphosphoryl-4-bromoaniline, C18H15BrNOP

“…The crystal structure of the title compound is similar to that observed in N-diphenylphosphorylaniline [1] and N-diphenylphosphoryl-2-cyanoaniline [2]. The phosphorus adopts ad istorted tetrahedral environment (figure, top), and the P-Oa nd P-Cdistances are within the normal ranges [1,2].…”

“…The phosphorus adopts ad istorted tetrahedral environment (figure, top), and the P-Oa nd P-Cdistances are within the normal ranges [1,2]. In addition, inter-molecular hydrogen bonding via P=O···H-Nexists in the title compound, thus resulting in azigzag arrangement in the lattice (figure, bottom).…”

Synthesis and characterization of new (N‐diphenylphosphino)‐isopropylanilines and their complexes: crystal structure of (Ph2P S)NHC6H44CH(CH3)2 and catalytic activity of palladium(II) complexes in the Heck and Suzuki cross‐coupling reactions

“…The resonances corresponding to complexes 1d-3d gradually disappeared with concomitant formation of Ph 2 P(O)H and Ph 2 P(O)OH as indentified by signals at δ = 21 and 35 ppm, respectively. [35] A single crystal of [(Ph 2 P S)NH-C 6 H 4 -4-CH(CH 3 ) 2 ] 2b suitable for X-ray diffraction studies was obtained by slow diffusion of diethyl ether into solution of the compound in dichloromethane.…”

New chiral phosphinite ligands with C2‐symmetric axis and their possible applications in Ru‐catalyzed asymmetric transfer hydrogenation

“…[36 -38] The 31 P-{ 1 H} NMR spectra also display formation of PPh 2 PPh 2 and P(O)Ph 2 PPh 2 , as indicated by signals at about δ −15.0 ppm as singlet and δ 37.2 ppm and δ −21.6 ppm as doublets with 1 J (PP) 224 Hz, respectively. [39] These by-products were easily eliminated by washing the residue with copious amounts of dry diethyl ether. Solutions of 1 and 2 in CDCl 3 , prepared under anaerobic conditions, are unstable and decompose gradually to give oxide and bis(diphenylphosphino)monoxide [P(O)Ph 2 PPh 2 ] derivatives.…”