Reactions of the hexachlorocyclodiphosphazane [MeNPCl3]2 with primary aromatic amines: formation of highly basic bisphosphinimines

Abstract

Reactions of hexachlorocyclodiphosphazane [ MeNPCI,], with primary aromatic amines afforded the bisphosphinimine hydrochlorides [(RNH),(RN)PN(Me)P(NHMe)(NHR),] 'CI-( R = Ph 1, C,H,Me-4 2 or C,H,OMe-4 3). Dehydrochlorination of 2 and 3 by methanolic KOH yielded highly basic bisphosphinimines [(RNH),(RN)PN(Me)P(NMe)(NHR),]( R = C,H,Me-4 4 or C,H,OMe-4 5). Compounds 1-5 have been characterised by elemental analysis and IR and N M R (lH, 13C, "P)

Taming the germyliumylidene [CIGe:]+ and germathionium [CIGeS]+ ions by donor–acceptor stabilization using 1,8-bis(tributylphosphazenyl)naphthalene

“…The Ge-S bond distance (2.066(1) Å ) in 3 is close to those of GeQS bonds stabilized by an intramolecular donor (ranging from 2.049(3) Å to 2.063(3) Å ), [11][12][13] but shorter than the reported Ge-S single bond distance (2.239(1) Å ), 14 implying the ylide nature of the GeQS moiety as depicted in Scheme 3. Similarly, the mean P-N distance of 1.668 Å in 3 lies between those of the P-N single bonds (1.75-1.80 Å ) 9 and PQN double bonds (1.51-1.57 Å ), 10 reflecting also the ylide nature of the PQN moieties. Presumably, the combination of such resonance stabilisation enables the isolation of the elusive chlorogermathionium cation [ClGeQS] + as a complex.…”

“…1). The second Cl The latter P-N distances lie between those of P-N single (1.75-1.80 Å ) 9 and double bonds (1.51-1.57 Å ), 10 exhibiting the delocalization of the positive charge in the cation of 2 in both PQN ylide moieties.…”

The Elusive Silyliumylidene [ClSi:]+ and Silathionium [ClSiS]+ Cations Stabilized by Bis(Iminophosphorane) Chelate Ligand

“…Both SiN bond distances in 2 are almost identical (1.847(3) and 1.835(3) Å) and marginally shorter than those in [PhC(N t Bu) 2 SiCl] (1.870(2) Å) 7c. The P1N1 (1.666(3) Å) and P2N2 bond lengths (1.659(3) Å) are also similar and range between those of PN single bonds (1.75–1.80 Å)12a and PN double bonds (1.51–1.57 Å),12b thus suggesting that the positive charge in the cation of 2 should be delocalized on both PN ylide moieties (Scheme ). In comparison with the 31 P NMR spectra of its precursors [ 1⋅ HBr] ( δ =41 ppm) and 1 ( δ =11 ppm), compound 2 shows a downfield‐shifted signal at δ =57.7 ppm in the 31 P NMR spectrum recorded in [D 2 ]dichloromethane.…”

New main group ligands for complexation with transition and inner transition elements

“…The nitrogen atom connecting the two phosphorus centres chelated to the metal in 26b deviates considerably from planar geometry whereas the other nitrogen atoms (and also the nitrogen atoms in 27) display planar geometry. The implications of the results for understanding the nature of the P-N bond are discussed elsewhere (Murugavel et al 1993(Murugavel et al , 1994. We have also synthesized a bicyclic phosphazane monoxide and its molybdenum earbonyl complex 2(~).…”