scholarly journals Hydrolysis of Element (White) Phosphorus under the Action of Heterometallic Cubane-Type Cluster {Mo3PdS4}

Molecules ◽  
2021 ◽  
Vol 26 (3) ◽  
pp. 538
Author(s):  
Airat M. Kuchkaev ◽  
Nikita Y. Shmelev ◽  
Aidar M. Kuchkaev ◽  
Aleksandr V. Sukhov ◽  
Vasily M. Babaev ◽  
...  

Reaction of heterometallic cubane-type cluster complexes—[Mo3{Pd(dba)}S4Cl3(dbbpy)3]PF6, [Mo3{Pd(tu)}S4Cl3(dbbpy)3]Cl and [Mo3{Pd(dba)}S4(acac)3(py)3]PF6, where dba—dibenzylideneacetone, dbbpy—4,4′-di-tert-butyl-2,2′-bipyridine, tu—thiourea, acac—acetylacetonate, py—pyridine, with white phosphorus (P4) in the presence of water leads to the formation of phosphorous acid H3PO3 as the major product. The crucial role of the Pd atom in the cluster core {Mo3PdS4} has been established in the hydrolytic activation of P4 molecule. The main intermediate of the process, the cluster complex [Mo3{PdP(OH)3}S4Cl3(dbbpy)3]+ with coordinated P(OH)3 molecule and phosphine PH3, have been detected by 31P NMR spectroscopy in the reaction mixture.

Molecules ◽  
2020 ◽  
Vol 25 (15) ◽  
pp. 3472
Author(s):  
Laura S. Van Rompuy ◽  
Nada D. Savić ◽  
Alvaro Rodriguez ◽  
Tatjana N. Parac-Vogt

The hydrolysis of the iron-binding blood plasma glycoprotein transferrin (Tf) has been examined at pH = 7.4 in the presence of a series of Zr-substituted polyoxometalates (Zr-POMs) including Keggin (Et2NH2)10[Zr(PW11O39)2]∙7H2O (Zr-K 1:2), (Et2NH2)8[{α-PW11O39Zr-(μ-OH) (H2O)}2]∙7H2O (Zr-K 2:2), Wells-Dawson K15H[Zr(α2-P2W17O61)2]·25H2O (Zr-WD 1:2), Na14[Zr4(α-P2W16O59)2(μ3-O)2(μ-OH)2(H2O)4]·57H2O (Zr-WD 4:2) and Lindqvist (Me4N)2[ZrW5O18(H2O)3] (Zr-L 1:1), (nBu4N)6[(ZrW5O18(μ–OH))2]∙2H2O (Zr-L 2:2)) type POMs. Incubation of transferrin with Zr-POMs resulted in formation of 13 polypeptide fragments that were observed on sodium dodecyl sulfate poly(acrylamide) gel electrophoresis (SDS-PAGE), but the hydrolysis efficiency varied depending on the nature of Zr-POMs. Molecular interactions between Zr-POMs and transferrin were investigated by using a range of complementary techniques such as tryptophan fluorescence, circular dichroism (CD), 31P-NMR spectroscopy, in order to gain better understanding of different efficiency of investigated Zr-POMs. A tryptophan fluorescence quenching study revealed that the most reactive Zr-WD species show the strongest interaction toward transferrin. The CD results demonstrated that interaction of Zr-POMs and transferrin in buffer solution result in significant secondary structure changes. The speciation of Zr-POMs has been followed by 31P-NMR spectroscopy in the presence and absence of transferrin, providing insight into stability of the catalysts under reaction condition.


1987 ◽  
pp. 349-359 ◽  
Author(s):  
Philip R. Pfeffer ◽  
Shu-I Tu ◽  
Walter V. Gerasimowicz ◽  
Richard T. Boswell

2019 ◽  
Vol 15 ◽  
pp. 1491-1504
Author(s):  
Stanislav V Lozovskiy ◽  
Alexander Yu Ivanov ◽  
Aleksander V Vasilyev

3-Methylbuta-1,2-dien-1-ylphosphonic acid derivatives (phosphorylallenes) [X2(O=)P–CR=C=CMe2, X = Cl, OMe, NR2, or SAr] undergo intramolecular cyclization into the corresponding 1,2-oxaphospholium ions in the Brønsted superacid TfOH. These cations have been thoroughly studied by means of NMR spectroscopy. The hydrolysis of superacidic solutions of these species afforded cyclic phosphonic acids and other phosphorus-containing compounds. Contrary to Brønsted acids, 3-methylbuta-1,2-dien-1-ylphosphonic dichloride [Cl2(O=)P–HC=C=CMe2] reacted with the Lewis acid AlCl3 in an intermolecular way forming noncyclic intermediates, which were investigated by NMR spectroscopy and DFT calculations. Hydrolysis of these species resulted in the formation of phosphoryl-substituted allyl alcohols and 1,3-butadienes. A strong coordination of the oxygen of the P=O group with AlCl3 prevented the formation of cyclic 1,2-oxaphospholium ions and played a crucial role in the different reactivity of such phosphorylallenes under the action of Brønsted or Lewis acids. Apart from that, the reaction of dichlorophosphorylallenes with arenes and AlCl3 led to products of hydroarylation of the allene system, phosphoryl-substituted alkenes and/or indanes. This is the first example of a Lewis acid-promoted intermolecular hydroarylation of allenes bearing electron-withdrawing substituents. Plausible reaction mechanisms have been proposed on the basis of the investigated reactions, and NMR analysis and DFT studies of the intermediate cationic species.


2009 ◽  
Vol 7 (1) ◽  
pp. 130-133 ◽  
Author(s):  
Abbas Tarassoli ◽  
Tahereh Sedaghat ◽  
Hamid-Reza Goudarzi

AbstractAminolysis of N3P3CI6 by an oxodiamine, bis-(2-ortho-aminophenoxyethyl) ether, has been carried out under various experimental conditions and new products with different architectures have been obtained. The reaction in diethyl ether when using a Na2CO3-water interface process gives the mono-BINO as major product. Reaction on Al2O3/KOH leads to the spirocyclic compound, while, when the reaction is carried out in toluene in the presence of NEt3, a mixture of mono- and di-BINO products are obtained. These new products have been characterized by IR, 1H and 31P NMR spectroscopy.


2020 ◽  
Author(s):  
Ashraf Ismail ◽  
Sanaz Molaye Moghaddam ◽  
Jean-Pierre MetabanzoulouSarya Aziz ◽  
Jacqueline Sedman ◽  
Mazen Bahadi

Author(s):  
Eliška Procházková ◽  
Hubert Hřebabecký ◽  
Radim Nencka ◽  
Martin Dračínský

1993 ◽  
Vol 34 (4) ◽  
pp. 397-404
Author(s):  
B. Moesgaard ◽  
I. Errebo Larsen ◽  
B. Quistorff ◽  
I. Therkelsen ◽  
V. Grøsfjeld Christensen ◽  
...  

2021 ◽  
Author(s):  
Dahiana Andrea Avila Salazar ◽  
Peter Bellstedt ◽  
Atsuhiro Miura ◽  
Yuki Oi ◽  
Toshihiro Kasuga ◽  
...  

Phosphate glass dissolution can be tailored via compositional and subsequent structural changes, which is of interest for biomedical applications such as therapeutic ion delivery. Here, solid-state 31P nuclear magnetic resonance...


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