Mono and bis[N-aryl(benzyl)]amides of phosphorylacetic acids. One-pot synthesis and extraction of actinides from nitric acid solutions

Abstract

A one pot synthetic route to phosphorylacetic acid N aryl(alkylaryl)amides, including those containing two phosphorylmethylcarbamoyl moieties attached to the arene framework, has been developed. The method is based on reactions of amines with the corresponding acid chlorides generated in situ with the use of phosphorus trichloride as a mild chlorinating agent. The compositions and structures of the compounds obtained and their extraction ability to ward Am III were determined. Suggestions were made about the compositions of the extracted complexes with phosphorylacetic acid N aryl(alkylaryl)amides.

Coordination Behavior of N,N′‐Bis(diisopropylphosphinoacetyl)‐o‐phenylenediamide with NiII and CuI Ions

“…In addition, the C–C bond lengths [1.382(3)–1.405(3) Å] of the six‐membered ring in [Cu I (H 2 L)Br] suggest a high degree of aromaticity. Furthermore, the N1–C7 and N2–C15 bond lengths [1.355(3)–1.364(3) Å] are comparable to those in the reported N , N′ ‐1,2‐phenylenebis[2‐(diphenylphosphinyl)acetamide] structure [1.365(4) and 1.356(4) Å, respectively] . Overall, these structural observations led to the assignment of H 2 L in [Cu I (H 2 L)Br] as N , N′ ‐bis(diisopropylphosphinoacetyl)‐ o ‐phenylenediamide.…”

“…In contrast to the tetradentate coordination mode of L 2– in [Ni II (L)], the H 2 L ligand in [Cu I (H 2 L)Br] presents a bidentate coordination mode, wherein the N atoms do not interact with the Cu atom, suggesting a flexible coordination mode of the (H 2 )L ligand in response to different metal ions. The N1–C1 [1.431(3) Å] and N2–C6 bond lengths [1.410(3)–1.412(3) Å] in [Cu I (H 2 L)Br] indicate a single bond character for the N–C bonds . In addition, the C–C bond lengths [1.382(3)–1.405(3) Å] of the six‐membered ring in [Cu I (H 2 L)Br] suggest a high degree of aromaticity.…”

Direct phosphorylation in the synthesis of new bis(phosphorylamino)pyridine ligands

“…1 Moreover, the introduction of additional phosphoryl groups in many cases makes it possible to increase considerably (sometimes by dozens of times) the efficiency of extraction of rare-earth metals from liquid radioactive wastes. 2 It is well known that poly(diphenylphosphoryl)alkanes and poly(diphenylphosphorylmethyl)arenes are used for extraction of tetra-and hexavalent actinides and lanthanides; 1 at the same time, trivalent transition metals are extracted with them much poorer. However, polydentate nitrogen heterocycles -tripyridyltriazines, terpyridines, bis(benzimidazolyl)pyridines, bis(benzothiazolyl)pyridines and, especially, polyalkyl-substituted 2,6-bis-(1,2,4-triazin-3-yl)pyridines -are much more efficient ligands for concentrating trivalent radionuclides.…”

Crystal structures of two bis-carbamoylmethylphosphine oxide (CMPO) compounds

“…Of these, seven structures have two or more CMPO groups tethered to one another via an organic scaffold. The most similar structures to compound (I) are CIWFAR (Ouizem et al, 2014) and SISLIQ (Artyushin et al, 2006). Both structures use an aromatic ring as the scaffold to present two phenyl-substituted CMPO groups.…”