Hydrogen‐Atom Tunneling in Metaphosphorous Acid

Qian, Weiyu; Chu, Xianxu; Song, Chao; Wu, Zhuang; Jiao, Mengqi; Zou, Bin; Rauhut, Guntram; Tew, David P.; Wang, Lina; Zeng, Xiaoqing

doi:10.1002/chem.202000844

Cited by 14 publications

(5 citation statements)

References 74 publications

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“…have generated considerable scientific interest due to their potential as phosphorylation/phosphonylation reagents − as well as their participation as intermediates/final products of combustion reactions involving warfare agents and flame retardants. , Dioxyphosphorane ( 1 , Figure ) and cis / trans -alkoxyphosphanone ( 2 , 3 ) are the structural isomers that these molecules are capable of adopting. The former, formally a P(V) species, is thermodynamically more favorable for all species regardless of the nature of the R substituent − ,− with the exception of the parent compound (i.e., R = H). − In fact, parent dioxophosphorane 1a has been predicted to be more than 40 kJ/mol less stable than the cis-isomer of hydroxyphosphanone ( 2a ), − and it was then not surprising that this least thermodynamically stable isomer (i.e., HPO 2 ) was only recently detected via infrared spectroscopy among several products formed during 193/266 nm laser photolysis of 2a in the Ar matrix at 2.8 K …”

Section: Introductionmentioning

confidence: 99%

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO₂P Source

et al. 2022

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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·PHO 2 . 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.

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Section: Introductionmentioning

confidence: 99%

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO₂P Source

et al. 2022

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“…The photolysis of cis ‐HOPO [9] in a solid Ar‐matrix was first performed by using a 266 nm laser. The resulting IR difference spectrum (Figure 1 A) shows the depletion of cis ‐HOPO (a, 3555.4/3548.4, 1252.6, 904.5, 841.5, and 523.9/517.4 cm −1 ) [9a] and the appearance of . PO 2 (d, 1325.6 cm −1 ) [22] .…”

Section: Figurementioning

confidence: 99%

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

et al. 2020

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Phosphorus monoxide (CPO) is a key intermediate in phosphorus chemistry, and its association with the hydroxyl radical (COH) to yield metaphosphorous acid (cis-HOPO) contributes to the chemiluminescence in the combustion of phosphines. When photolyzing cis-HOPO in an Ar-matrix at 2.8 K, the simplest dioxophosphorane HPO 2 and an elusive hydroxyl radical complex (HRC) of CPO form. This prototypical radical-radical complex reforms into cis-HOPO at above 12.0 K by overcoming a barrier of 0.28 AE 0.02 kcal mol À1. The vibrational spectra of this HRC and its D-and 18 Oisotopologues suggest a structure of COH•••OPC, for which a triplet spin multiplicity with a binding energy of À3.20 kcal mol À1 has been computed at the UCCSD(T)-F12a/aug-cc-pVTZ level.

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“…Tunneling is a quantum mechanical phenomenon that describes how particles permeate through potential energy barriers. , The occurrence of tunneling in chemical reactions used to be largely ignored, and the conceptual framework to understand chemical reactivity has been inferred from the transition state theory (TST), which assumes that nuclei behave according to classical mechanics. , For many years, tunneling relevance to chemical reactivity has only been acknowledged in the field of chemical kinetics, where tunneling appears as a correction factor in the TST calculations of rate constants (in particular for reactions involving the transfer of hydrogen atoms or ions). , However, recent evidence has shown that tunneling not only is more common than previously thought (even occurring for reactions involving the motion of heavy atoms such as carbon) but also can have profound consequences on the chemical reaction outcome, casting doubts on the validity of the TST principles. − …”

Section: Introductionmentioning

confidence: 99%

Simultaneous Tunneling Control in Conformer-Specific Reactions

et al. 2022

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We present here a new example of chemical reactivity governed by quantum tunneling, which also highlights the limitations of the classical theories. The syn and anti conformers of a triplet 2-formylphenylnitrene, generated in a nitrogen matrix, were found to spontaneously rearrange to the corresponding 2,1-benzisoxazole and imino-ketene, respectively. The kinetics of both transformations were measured at 10 and 20 K and found to be temperature-independent, providing clear evidence of concomitant tunneling reactions (heavy-atom and Hatom). Computations confirm the existence of these tunneling reaction pathways. Although the energy barrier between the nitrene conformers is lower than any of the observed reactions, no conformational interconversion was observed. These results demonstrate an unprecedented case of simultaneous tunneling control in conformer-specific reactions of the same chemical species. The product outcome is impossible to be rationalized by the conventional kinetic or thermodynamic control.

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Hydrogen‐Atom Tunneling in Metaphosphorous Acid

Cited by 14 publications

References 74 publications

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO₂P Source

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO₂P Source

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

Simultaneous Tunneling Control in Conformer-Specific Reactions

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Hydrogen‐Atom Tunneling in Metaphosphorous Acid

Cited by 14 publications

References 74 publications

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO2P Source

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO2P Source

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

Simultaneous Tunneling Control in Conformer-Specific Reactions

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Product

Resources

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Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO₂P Source

Carbodiphosphorane-Stabilized Parent Dioxophosphorane: A Valuable Synthetic HO₂P Source