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Journal ArticleDOI

Building a Lewis Acidic Phosphorus

TL;DR: Using the σ and п-donating properties of carbodiphosphorane ligands, this article synthesized a phosphorus (III)-containing dication, which is observed to undergo interesting reactivity with PMe3, H2O and MeOH.
Abstract: Using the σ- and п-donating properties of carbodiphosphorane ligands, we recently synthesized a phosphorus (III)-containing dication. It is observed to undergo interesting reactivity with PMe3, H2O and MeOH.

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Citations
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Journal ArticleDOI
TL;DR: In this paper, the synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)2C)P(NiPr2)]2+ (3a2+) have been investigated.

20 citations

Journal ArticleDOI
TL;DR: The syntheses and application of AgI carbone complexes as carbone transfer agents are reported and the first experimental evidence for two-sulfur-stabilized carbones behaving as four-electron donors is provided.
Abstract: Bis(sulfane)carbon(0) (BSC; Ph2 S→C←SPh2 (1)) is successfully synthesized by deprotonation of the corresponding protonated salt 1⋅HTfO. The diprotonated salt 1⋅(HTfO)2 as the starting material can be also easily accessed by the deimination of iminosulfane(sulfane)carbon(0) (iSSC)⋅HBF4 . Density functional theory calculations revealed the peculiar electronic structure of 1, which has two lone pairs of electrons at the central carbon atom. The largest proton affinities (PA(1): 297.5 kcal mol-1 ; PA(2): 183.7 kcal mol-1 ) and the highest energy levels of the HOMOs (HOMO: -4.89 eV; HOMO-1: -5.02 eV) for 1 among the two-sulfur-stabilized carbones clearly indicate the strong donor ability of carbon center stabilized by two SII ligands. The donating ability of these lone pairs of electrons is demonstrated by the C-diaurated and C-proton-aurated complexes, which provide the first experimental evidence for two-sulfurstabilized carbones behaving as four-electron donors. Furthermore, the syntheses and application of AgI carbone complexes as carbone transfer agents are also reported.

10 citations

Journal ArticleDOI
TL;DR: The reactivity of nucleophilic carbodiphosphorane and carbodicarbene towards various dichlorophosphines has been explored and the use of MeN(PCl2)2 resulted in a unique P-N bond cleavage that, according to computational studies, occurred via an SN2'-like mechanism.

10 citations

Journal ArticleDOI
TL;DR: In this paper , electron-rich hexaphenyl carbodiphosphorane (CDP) was used to stabilize the least thermodynamically favorable isomer of HO2P to yield monomeric CDP·PHO2.
Abstract: Introducing a small phosphorus-based fragment into other molecular entities via, for example, phosphorylation/phosphonylation is an important process in synthetic chemistry. One of the approaches to achieve this is by trapping and subsequently releasing extremely reactive phosphorus-based molecules such as dioxophosphoranes. In this work, electron-rich hexaphenylcarbodiphosphorane (CDP) was used to stabilize the least thermodynamically favorable isomer of HO2P to yield monomeric CDP·PHO2. The title compound was observed to be a quite versatile phosphonylating agent; that is, it showed a great ability to transfer, for the first time, the HPO2 fragment to a number of substrates such as alcohols, amines, carboxylic acids, and water. Several phosphorous-based compounds that were generated using this synthetic approach were also isolated and characterized for the first time. According to the initial computational studies, the addition-elimination pathway was significantly more favorable than the corresponding elimination-addition route for "delivering" the HO2P unit in these reactions.

5 citations

Journal ArticleDOI
TL;DR: This oxygen insertion appears to be the first example of a Baeyer-Villiger oxidation involving O-py involving pyridine N-oxide, and was identified as an analogue of the elusive Criegee intermediate as it underwent oxygen insertion into the P-C bond through a mechanism usually observed for Baeyersvilliger oxidations.
Abstract: The reactivity of phosphenium dication [(Ph3P)2C-P-NiPr2](2+), 1(2+), towards pyridine N-oxide (O-py) has been investigated. The resulting oxophosphonium dication [(Ph3P)2C(NiPr2)P(O)(O-py)](2+), 2(2+), was surprisingly stabilized by a less nucleophilic O-py ligand instead of pyridine (py). This compound was then identified as an analogue of the elusive Criegee intermediate as it underwent oxygen insertion into the P-C bond through a mechanism usually observed for Baeyer-Villiger oxidations. This oxygen insertion appears to be the first example of a Baeyer-Villiger oxidation involving O-py.

5 citations

References
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Journal ArticleDOI
TL;DR: Synthese, structure et caracterisation du (1,3-bis [1-adamantyl]-2, 3-dihydro)-2,carbenoimidazole prepare par deprotonation du chlorure de (1 3-bis] [1]- imidazolium as discussed by the authors.
Abstract: Synthese, structure et caracterisation du (1,3-bis [1-adamantyl]-2,3-dihydro)-2-carbenoimidazole prepare par deprotonation du chlorure de (1,3-bis [1-adamantyl]) imidazolium

3,414 citations

Book
01 Jan 1972
TL;DR: In this article, inorganic chemistry principles of structure and reactivity are presented. But, they do not cover how to use these principles in the design of products, and they are not available in any type of product.
Abstract: INORGANIC CHEMISTRY PRINCIPLES OF STRUCTURE AND REACTIVITY JAMES E HUHEEY PDF Are you looking for Ebook inorganic chemistry principles of structure and reactivity james e huheey PDF ? You will be glad to know that right now inorganic chemistry principles of structure and reactivity james e huheey PDF is available on our online library. With our online resources, you can find inorganic chemistry principles of structure and reactivity james e huheey or just about any type of ebooks, for any type of product.

2,814 citations


Additional excerpts

  • ...2).(86) Additionally, similar thermodynamic parameters (∆H= -37....

    [...]

Journal ArticleDOI
TL;DR: Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid/Lewis base adducts, but both the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available to carry out unusual reactions.
Abstract: Sterically encumbered Lewis acid and Lewis base combinations do not undergo the ubiquitous neutralization reaction to form "classical" Lewis acid/Lewis base adducts. Rather, both the unquenched Lewis acidity and basicity of such sterically "frustrated Lewis pairs (FLPs)" is available to carry out unusual reactions. Typical examples of frustrated Lewis pairs are inter- or intramolecular combinations of bulky phosphines or amines with strongly electrophilic RB(C(6)F(5))(2) components. Many examples of such frustrated Lewis pairs are able to cleave dihydrogen heterolytically. The resulting H(+)/H(-) pairs (stabilized for example, in the form of the respective phosphonium cation/hydridoborate anion salts) serve as active metal-free catalysts for the hydrogenation of, for example, bulky imines, enamines, or enol ethers. Frustrated Lewis pairs also react with alkenes, aldehydes, and a variety of other small molecules, including carbon dioxide, in cooperative three-component reactions, offering new strategies for synthetic chemistry.

1,621 citations

Book
01 Jan 1963

1,077 citations


"Building a Lewis Acidic Phosphorus" refers background in this paper

  • ...One of the most characteristic of all reactions involving carbocations is the Friedel Crafts acylation of aromatics.(157) Recognising that the intermediate phosphorus dication (3e or 3g) is a potential analogue of a carbocation, an electrophilic aromatic...

    [...]

Journal ArticleDOI
TL;DR: To overcome the problem of excessive steric hindrance, Glorius and co-workers have successfully developed ligands with “flexible steric bulk” using the conformational flexibility of cyclohexane.
Abstract: The availability of catalysts to perform specific transformations is critical for both industry and academia. Over the years, the success of homogeneous catalysis can be attributed largely to the development of a diverse range of ligand frameworks that have been used to tune the behavior of a variety of metal-containing systems. Advances in ligand design have allowed not only for improvements of known processes in terms of scope, mildness, and catalyst loadings, but also for the discovery of new selective reactions. A good illustration is given by palladium-catalyzed coupling reactions, which are applied to a wide area of endeavors ranging from synthetic organic chemistry to materials science.[1] For these catalytic processes, which represent some of the most powerful and versatile tools available for synthetic chemists, major advances have recently been reported thanks to the use of bulky, electron-rich, phosphines A and cyclic diaminocarbenes (N-heterocyclic carbenes (NHCs)) B (Figure 1).[2] These ligands stabilize the active catalytic species, and accelerate the important catalytic steps, namely oxidative addition, transmetallation, and reductive elimination. On the other hand, excessive steric hindrance can present some drawbacks for the coupling of bulky reactants.[3] To overcome this problem Glorius and co-workers have successfully developed ligands with “flexible steric bulk” using the conformational flexibility of cyclohexane.[4]

841 citations