Reaction of alkali-metal 2,4-dinitrophenolates with 1,4,7,10-tetra(diphenylphosphinylethyl)-1,4,7,10-tetraazacyclododecane

Sinyavskaya, E. I.; Tsymbal, L. V.; Yatsimirskii, K. B.; Pisareva, S. A.; Medved, T. Ya.; Кабачник, М. И.

doi:10.1007/bf00952866

Cited by 5 publications

(2 citation statements)

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“…Nevertheless, a few chelating ligands bearing phosphine oxide moieties have been reported for copper(II), − demonstrating a certain reciprocal affinity. With polyazamacrocycles, to the best of our knowledge, only two examples have been reported so far, namely, ethyl- or methyldiphenylphosphoryl tetrasubstituted cyclen, , for the coordination of alkali metal ions and divalent cations of groups 9–12, respectively, but with no demonstrated selectivity. Thus, we sought to combine the copper(II) coordination properties of both cyclam and phosphine oxide side arms and report herein the synthesis of the novel te1po Ph ligand and its te2po Ph congener.…”

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confidence: 99%

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A Phosphine Oxide-Functionalized Cyclam as a Specific Copper(II) Chelator

et al. 2023

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Although cyclam-based ligands are among the strongest copper(II) chelators available, they also usually present good affinity for other divalent cations [Zn(II), Ni(II), and Co(II)], with no copper(II)-specific cyclam ligands having been described so far. As such a property is highly desirable in a wide range of applications, we present herein two novel phosphine oxide-appended cyclam ligands that could be efficiently synthesized through Kabachnik−Fields type reactions on protected cyclam precursors. Their copper(II) coordination properties were closely studied by different physicochemical techniques [electron paramagnetic resonance (EPR) and ultraviolet−visible (UV−vis) spectroscopies, X-ray diffraction, and potentiometry]. The mono-(diphenylphosphine oxide)-functionalized ligand demonstrated a copper(II)-specific behavior, unprecedented within the cyclam family of ligands. This was evidenced by UV−vis complexation and competition studies with the parent divalent cations. Density functional theory calculations also confirmed that the particular ligand geometry in the complexes strongly favors copper(II) coordination over that of competing divalent cations, rationalizing the specificity observed experimentally.

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Section: Introductionmentioning

confidence: 99%

“…31 P NMR (CDCl 3 , 202 MHz, 328 K, H 3 PO 4 ) δ 34.4 (P�O); ESI-HR-MS (positive, H 2 O) m/z calcd for [C 36 H 47 N 4 O 2 P 2 ] 629.3169, found [M + H] + 629.3169, calcd for [C 36 H 48 N 4 O 2 P 2 ] 2+ 315.1620, found [M + 2H] 2+ 315.1625. Synthesis of [Cu(te2po Ph )](ClO 4 ) 2 .…”

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A Phosphine Oxide-Functionalized Cyclam as a Specific Copper(II) Chelator

et al. 2023

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Aminophosphine Oxides: A Platform for Diversified Functions

2017

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This review summarizes significant contributions reported on aminophosphine oxides (AmPOs), specifically those containing at least one amino group present as amino substituents on α- and β-carbons including direct P-N bond containing molecules. AmPOs have additional 'N' site(s), including highly basic 'P=O' groups, and these features make favor smooth and unexpected behavior. The most striking manifestations of flexibility of AmPOs are that they are exciting ligand systems for the coordination chemistry of actinides, and their involvement in catalytic organic reactions including enantioselective opening of meso-epoxides, addition of silyl enol ethers, allylation with allyltributylstannane, etc. The diverse properties of the AmPOs and their metal complexes demonstrate both the scope and complexity of these systems, depending on the basicity of phosphoryl group, and nature of the substituents on the pentavalent tetracoordinate phosphorus atom and metal. Two components key to understanding the challenges of actinide separations are detailed here, namely, previously described separation methods, and recent investigations into the fundamental coordination chemistry of actinides. Both are aimed at probing the critical features necessary for improved selectivity of separations. This review leads to the conclusion that, although many AmPOs have already been discovered and developed over the past century, many opportunities nevertheless exist for further developments towards new extraction processes and new catalytic materials by fine tuning the electronic and steric properties of substituents on the central phosphorus atom.

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