Properties and Reactions of Phosphonic and Phosphinic Acids and their Derivatives

Edmundson, R. S.

doi:10.1002/9780470682531.pat0066

Cited by 4 publications

(5 citation statements)

References 645 publications

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“…Phosphinic acid requires higher temperatures to dissolve the CdO compared to phosphonic acid. This is most likely due to the lower acidity of alkylphosphinic acid (p K a in H 2 O ≈ 3.1) compared to alkylphosphonic acid (p K a in H 2 O ≈ 2.4 and 7.7) . After dissolution of CdO, TOP-Se is injected at 300 °C, and CdSe quantum dots are rapidly formed (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…This is most likely due to the lower acidity of alkylphosphinic acid (pKa in H 2 O ≈ 3.1) compared to alkylphosphonic acid (pKa in H 2 O ≈ 2.4 and 7.7). 54 After dissolution of CdO, TOP-Se is injected at 300 °C and CdSe quantum dots are rapidly formed (Figure 1). After 10 minutes the reaction mixture is cooled down and the nanocrystals are easily purified by precipitation/redispersion cycles with acetone/toluene as antisolvent/solvent.…”

Section: Productsmentioning

confidence: 99%

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Monoalkyl Phosphinic Acids as Ligands in Nanocrystal Synthesis

et al. 2022

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Ligands play a crucial role in the synthesis of colloidal nanocrystals. Nevertheless, only a handful molecules are currently used, oleic acid being the most typical example. Here, we show that mono-alkyl phosphinic acids are another interesting ligand class, forming metal complexes with a reactivity that is intermediate between the traditional carboxylates and phosphonates.We first present the synthesis of n-hexyl, 2-ethylhexyl, n-tetradecyl, n-octadecyl, and oleyl phosphinic acid. These compounds are suitable ligands for high-temperature nanocrystal synthesis (240-300°C) since, in contrast to phosphonic acids, they do not form anhydride oligomers. Consequently, CdSe quantum dots synthesized with octadecylphosphinic acid are conveniently purified, and their UV-Vis spectrum is free from background scattering. The CdSe nanocrystals have a low polydispersity and a photoluminescence quantum yield up to 18%. Furthermore, we could synthesize CdSe and CdS nanorods using phosphinic acid ligands, with high shape purity. We conclude that the reactivity towards TOP-S and TOP-Se precursors decreases in the series: cadmium carboxylate > cadmium phosphinate > cadmium phosphonate.By introducing a third and intermediate class of surfactants, we enhance the versatility of surfactant-assisted syntheses.

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Section: Resultsmentioning

confidence: 99%

Section: Productsmentioning

confidence: 99%

Monoalkyl Phosphinic Acids as Ligands in Nanocrystal Synthesis

et al. 2022

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“…In this study, we investigate X-type ligand exchanges with monoalkyl phosphinic acids on both metal oxide (HfO 2 ) and metal chalcogenide (CdSe and ZnS) NCs. Given their intermediate acidity, monoalkyl phosphinic acids (p K a ≈ 3.08) are expected to bind to surfaces with an affinity between carboxylic and phosphonic acids. , We designed two sets of exchange experiments to test this hypothesis. A first exchange reaction is carefully monitored by titrating oleate-capped NCs with 6-(hexyloxy)hexylphosphinic acid.…”

Section: Introductionmentioning

confidence: 99%

Binding Affinity of Monoalkyl Phosphinic Acid Ligands toward Nanocrystal Surfaces

et al. 2023

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We recently introduced monoalkyl phosphinic acids as a ligand class for nanocrystal (NC) synthesis. Their metal salts have interesting reactivity differences compared to metal carboxylates and phosphonates and provide a cleaner work-up compared to phosphonates. However, little is known about the surface chemistry of NCs with monoalkyl phosphinate ligands. Here, we probe the relative binding affinity of monoalkyl phosphinate ligands with respect to other X-type ligands. We perform competitive ligand exchange reactions with carboxylate and phosphonate ligands at the surface of hafnia, cadmium selenide, and zinc sulfide NCs. We monitor the ligand shell composition by solution 1 H and 31 P NMR spectroscopy. Using a monoalkyl phosphinic acid with an ether functionality, we gain an additional NMR signature, apart from the typical alkene resonance in oleic acid and oleylphosphonic acid. We find that carboxylate ligands are easily exchanged upon exposure to monoalkyl phosphinic acids, whereas an equilibrium is reached between monoalkyl phosphinates and phosphonates, slightly in the favor of phosphonate (K = 2). Phosphinic acids have thus an intermediate binding affinity between carboxylic acids and phosphonic acids for all the NCs studied. These results enable the sophisticated use of monoalkyl phosphinic acids for NC synthesis and for post-synthetic surface engineering.

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“…The phosphinate group also falls between carboxylates and phosphonates in terms of Pearson’s theory of hard and soft acids and bases [ 31 ]. The acidity of phosphinic acids also lies between the acidity of carboxylic and phosphonic acids [ 32 ].…”

Section: Introductionmentioning

confidence: 99%

Influence of the Substituent’s Size in the Phosphinate Group on the Conformational Possibilities of Ferrocenylbisphosphinic Acids in the Design of Coordination Polymers and Metal–Organic Frameworks

Shekurov,

Khrizanforov,

Bezkishko

et al. 2023

IJMS

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This paper illustrates how the size and type of substituent R in the phosphinate group of ferrocenyl bisphosphinic acids can affect conformational possibilities and coordination packing. It also demonstrates that H-phosphinate plays a key role in variational mobility, while Me- or Ph- substituents of the phosphinate group can only lead to 0D complexes or 1D coordination polymer. Overall, this paper provides valuable insights into the design and construction of coordination polymers based on ferrocene-contained linkers. It sheds light on how different reaction conditions and substituents can affect conformational possibilities and coordination packing, which could have significant implications for developing new polymers with unique properties.

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Properties and Reactions of Phosphonic and Phosphinic Acids and their Derivatives

Abstract: Introduction The Role of the Phosphoryl ( P  Z )( Z = O , S , Se OR Te )Group Cleavage of the Phosphorus—Carbon Bond Reactions and Properties of the Carbon Ligands: The Functional Groups… Show more

Cited by 4 publications

References 645 publications

Monoalkyl Phosphinic Acids as Ligands in Nanocrystal Synthesis

Monoalkyl Phosphinic Acids as Ligands in Nanocrystal Synthesis

Binding Affinity of Monoalkyl Phosphinic Acid Ligands toward Nanocrystal Surfaces

Influence of the Substituent’s Size in the Phosphinate Group on the Conformational Possibilities of Ferrocenylbisphosphinic Acids in the Design of Coordination Polymers and Metal–Organic Frameworks

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