Quantum chemical study of the mechanism of the reaction of tetraphosphorus with alcohol in the coordination sphere of copper(II)

Dorfman, Ya. A.; Abdreimova, Rumiya R.; Doroshkevich, D. M.

doi:10.1007/bf01373404

Cited by 3 publications

(4 citation statements)

References 3 publications

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“…The CNDO calculations suggest that both P 4 a n d R O H a r e activated in coordination sphere of Cu(II) ion building up neat intraligand charge separations that favor their further intramolecular coupling step. T h u s , w h i l e t h e t e t r a h e d r a l P 4 molecule undergoes a severe pyramidal distortion, weakens the P-P bond coordinated to the metal, and ac c um ul ate s the re in a po si tive ch arge , the ROH ligand hyperpolarizes at the O-H bond and, with the assistance of the cis arranged X ligand, deprotonates converting to an alkoxyde ligand [3,4]. Once this positive electric and steric situation has been set up, the intramolecular nucleophilic attack of the OR ligand to the closest of the two positively charged P-atoms eventually affords the P 4 (OR) ligand.…”

Section: Resultsmentioning

confidence: 99%

“…The stirring of the P 4 dissolved in the mixture of C 6 H 6 /CCl 4 solvents with aqueous solution of CuSO 4 under inert atmosphere at 40-60 o C readily gives a gray sediment consisting of the copper salts of phosphorous and phosphoric acids together with elementary copper [2]. The reduction of Cu (II) compounds by P 4 in alcoholic solutions has not yet properly investigated, only its theoretical modeling has been described in a series of dedicated papers [3,4]. The CNDO calculations of the model intermediate complexes (X = Cl, Br, OH; L = H 2 O, CH 3 OH, NH 3 ; m 3) suggest that molecules of P 4 and alcohol are in coordination sphere of Cu(II) ion towards the P-O coupling with each other irrespectively on the nature of the X and L ligands [3,4].…”

Section: Introductionmentioning

confidence: 99%

“…The reduction of Cu (II) compounds by P 4 in alcoholic solutions has not yet properly investigated, only its theoretical modeling has been described in a series of dedicated papers [3,4]. The CNDO calculations of the model intermediate complexes (X = Cl, Br, OH; L = H 2 O, CH 3 OH, NH 3 ; m 3) suggest that molecules of P 4 and alcohol are in coordination sphere of Cu(II) ion towards the P-O coupling with each other irrespectively on the nature of the X and L ligands [3,4].…”

Section: Introductionmentioning

confidence: 99%

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Copper (II) Mediated Oxidative Alkoxylation of White Phosphorus. Communication 1.

Abdreimova¹,

Faizova²,

Karimova³

2010

Eur Chem Tech J

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White phosphorus has been oxidized by copper (II) acetylacetonate, halides or carboxylates in aliphatic alcohols to yield dialkyl phosphates and trialkyl phosphates under inert atmosphere and mild reaction conditions. Trialkyl phosphite has been observed as unstable organophosphorus intermediate, which is being converted into the main reaction products. In the case of methanolic solutions, the derivatives of two step acidolysis of dimethyl phosphite, monomethyl phosphite and phosphorous acid, have been additionally detected among the reaction products. The influence of the copper (II) oxidants on the kinetics of accumulation and transmutation of organophosphorus products has been explored. The order of oxidative ability of the copper (II) compounds has been established. The major steps of the reaction including (i) the coordination of white phosphorus and alcohol to metal ion and (ii) the redox decomposition of this intermediate complex accompanied by reducing elimination of elementary copper and formation of organophosphorus product have been also suggested.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Copper (II) Mediated Oxidative Alkoxylation of White Phosphorus. Communication 1.

Abdreimova¹,

Faizova²,

Karimova³

2010

Eur Chem Tech J

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“…In the presence of the catalytic FeCl 3 -I 2 system, the stages of the oxidation of P 4 by I 2 followed by the reduction of Fe(III) by Iand the oxidation of Fe(II) by oxygen are supposed. It should be mentioned that the above stages of the complexation of reagents to Cu(II) and Fe(III) ions followed by the oxidative P-O coupling of white phosphorus to alcohol have been established and studied by the kinetic, potentiometric, thermodynamic, IR, ESR [2][3][4][5] and quantum chemical CNDO [8,9] methods. Dealkylation of P(OR) 3 (iii) occurs as a result of interaction with water or acid both generated in situ.…”

Section: Catalyst Fexmentioning

confidence: 99%

Catalytic Synthesis of the Esters of Phosphorus Acids from White Phosphorus and Aliphatic or Aromatic Alcohols

Abdreimova¹,

Faizova²,

Akbayeva³

et al. 2017

Eurasian Chem. Tech. J.

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The various esters of the phosphoric and phosphorous acids have been obtained directly from white phosphorus and aliphatic (or aromatic) alcohols under aerobic atmosphere in the presence of the CuX2 or FeX3 (X = Cl, NO3, C3H7CO2) salts. Irrespective of the variable nature of the used alcohols and catalysts, trialkyl(aryl) phosphates and dialkyl phosphites are a major products, whereas trialkyl(aryl) phosphites and dialkyl phosphates are a minor products of the phosphorylation process. Thanks to the presence of catalysts, the possible side reaction route of the radical chain oxidation of white phosphorus by oxygen to phosphorus oxides has been precluded. A comparison between the catalytic properties of CuX2 and FeX3 has been done. Although both of them have been found an efficient catalysts for the syntheses, the Cu(II) salts are active at 50-65 °C, whereas the Fe(III) based catalytic systems become competitive in terms of catalytic efficiency when reaction is carried out at 70-90 °C. Aromatic alcohols are characterised by less reactivity in this catalytic reaction as compared with an aliphatic ones. The same coordinative redox mechanism of the oxidative P-O coupling of P4 to ROH in the presence of both Cu(II) and Fe(III) catalysts has been proposed. Relevant steps of the catalytic cycle including the complexation of both white phosphorus and alcohol molecules to metal ion, the reduction of catalyst by white phosphorus, and the oxidation of reduced form of catalyst by oxygen have been also considered.

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Selective O-functionalization of phenolic α-amino acids with crown ethers bearing cyclophosphazene sub-units

et al. 2011

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Quantum chemical study of the mechanism of the reaction of tetraphosphorus with alcohol in the coordination sphere of copper(II)

Cited by 3 publications

References 3 publications

Copper (II) Mediated Oxidative Alkoxylation of White Phosphorus. Communication 1.

Copper (II) Mediated Oxidative Alkoxylation of White Phosphorus. Communication 1.

Catalytic Synthesis of the Esters of Phosphorus Acids from White Phosphorus and Aliphatic or Aromatic Alcohols

Selective O-functionalization of phenolic α-amino acids with crown ethers bearing cyclophosphazene sub-units

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