Étude expérimentale et théorique de la cinétique de l’alcoolyse de la liaison P–N extracyclique du 2-diméthylamino-4,4,5,5-tétraméthyl-1,3-dioxaphospholane monocyclique

Fliss, Outaf; Méjri, Alia; Essalah, Khaled; Boisdon, M. T.; Tangour, Bahoueddine

doi:10.1016/j.crci.2015.11.007

Cited by 5 publications

(6 citation statements)

References 21 publications

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“…The four-membered P 1 C 6 O 5 C 4 fragment is planar within 0.066(5)Å, and the O 7 atom deviates from this plane by À0.853(5)Å. The O 1 , O 2 , O 3 , C 3 , C 19 , C 25 and C 26 atoms deviate from the abovementioned fragment by the values of À0.699(5), 1.392(5), À0.949(5), 1.337 7, À0.579(7), À1.40(1) and 1.097(9) A, respectively.…”

Section: Resultsmentioning

confidence: 98%

“…Therefore, the synthesis, structure and chemical transformations of phosphoranes have attracted considerable attention. [20][21][22][23][24][25][26][27] Among the diverse synthetic methods for the preparation of phosphoranes, several general approaches based on the addition reactions of P(III)-derivatives to unsaturated systems, various reactions of tetracoordinated phosphorus and substitution reactions at P(V) 28,29 should be noted.…”

Section: Introductionmentioning

confidence: 99%

“…The conformation of the other ve-membered P 1 O 6 C 5 C 4 O 7 cycle of the rigid bicycloheptane system of molecule 14 is a slightly distorted envelope [four-membered P 1 O 6 C 5 C 4 fragment is planar within 0.044(3)Å, and the O 7 atom deviates from the above fragment by À0.851(2)Å]. The O 1 , O 2 , O 3 , C 3 , C19 , C25 and C…”

mentioning

confidence: 99%

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Synthesis, crystal structure and hydrolysis of novel isomeric cage (P–C/P–O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone

et al. 2016

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Synthesis, crystal structure and hydrolysis of novel isomeric cage (P–C/P–O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone

et al. 2016

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“…The monitoring of the variation in the internuclear distances of the active atoms at the influence zone of the transition state is a technique that has been, increasingly, used to discuss the reaction mechanism of an elementary step [21,[38][39][40]. During this elementary step, H1 was transferred from Ru to C2 and a σ bond was created between Ru and C3.…”

Section: Hydrogenation Mechanism With a Complex With Two Phosphinesmentioning

confidence: 99%

A DFT Study of the Hexene Hydrogenation Catalysed by the Complex RuH(CO)(Cl)(PCy3): Monophosphine vs Diphosphine Paths

Hosni

Tangour²,

Achour³

2019

Preprint

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A DFT study of hexene hydrogenation catalysed by the RuH(CO)(Cl)(PCy3)2 complex is presented. The investigation explores the feasibility of two different mechanisms: the first exploits a single phosphine complex and the second uses a two phosphines complex. The energy barriers involving a hydrogen transfer have a ten kcal.mol-1 higher than the one obtained through the single-phosphine mechanism. These results confirm the experimental hypothesis claiming that the departure of a phosphine is favourable at the beginning of the reaction which is the substitution of the catalyst model RuHCl(CO)(PMe3)2 by the real catalyst RuHCl(CO)(PCy3)2 shows no significant influence on the energetic barriers of hexene hydrogenation mechanism. The most important step of the mechanism is the kinetically determining step. The heterolytic cleavage of ruthenium-complexed H2 molecule leads to the generation of two Ru-H bonds and the oxidation of the ruthenium from Ru(II) to Ru(IV). The energy profile of this step is not relative to an elementary reaction because a shouldering is observed after the transition state. This results in an unusual gradient norm profile with five extrema. This is a direct consequence of the asynchronous nature of the different processes taking place during this step. In the case of the model complex RuHCl(CO)(IMes)(PMe3) with IMes = ( N , N '-bis( mesityl)imidazol-2-ylidene), an increase of the free enthalpy of activation is observed during the kinetically determining step, which is in agreement with the experimental work.

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“…The biphilic nature of phosphorus is illustrated in the oxidative addition of AH (alcohol or amine) on monocyclic P III compounds, leading to stable hydrido‐phosphoranes (Scheme 1). 11, 15–19 …”

Section: Introductionmentioning

confidence: 99%

New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

Méjri

Fliss

Essalah

et al. 2022

Int J of Quantum Chemistry

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Oxidative addition of aliphatic amine on monocyclic 2-R-1,3,2-dioxaphospholane (R = methyl or phenyl) leading to phosphoranes bearing a P H axial bond was investigated using a combined theoretical and experimental approach. The reaction followed first order kinetics for both reactants. The activation parameters were consistent with a concerted mechanism exhibiting stereo, enantio, and regio specificities.Systematic density functional theory studies including reactivity descriptors, structural parameters, determination of all possible phosphorane isomers, their transition states and their formation mechanisms were carried out to delineate the reaction pathway. Depending on the nature of the atom in the final apical position (H, N of the amine, or C of the methyl), three types of phosphoranes were identified. Energy profiles, using the intrinsic reaction coordinate technique for the formation of each isomer, were established. It was shown that the phosphorus biphilicity acts in three consecutive sequences, namely nitrogen nucleophilic attack leading to a supermolecule structure, nucleophilic behavior of phosphorus in the transition state zone of influence, and electrophilic approach of the nitrogen atom to complete the reaction. Phosphorane with an equatorial P H bond was found to be a kinetic product that transforms rapidly to the thermodynamically stable isomer with axial P H via two consecutive Berry pseudo-rotations. A new tool, referred to reactive internal reaction coordinates, was introduced to represent the reaction path more clearly.

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Étude expérimentale et théorique de la cinétique de l’alcoolyse de la liaison P–N extracyclique du 2-diméthylamino-4,4,5,5-tétraméthyl-1,3-dioxaphospholane monocyclique

Cited by 5 publications

References 21 publications

Synthesis, crystal structure and hydrolysis of novel isomeric cage (P–C/P–O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone

Synthesis, crystal structure and hydrolysis of novel isomeric cage (P–C/P–O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone

A DFT Study of the Hexene Hydrogenation Catalysed by the Complex RuH(CO)(Cl)(PCy3): Monophosphine vs Diphosphine Paths

New insights into phosphorus biphilicity: Stereochemistry of monocyclic aminophosphoranes formation

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