Some thermodynamic properties of phosphorus trifluoride

Finch, Arthur

doi:10.1002/recl.19650840404

Cited by 2 publications

(2 citation statements)

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“…We speculated that the use of phosphorus compounds would provide an alternative approach for the efficient capture of HF, principally because of the large P−F bond energy (119.4 kcal mol −1 ). 11 The kinetically stabilized 1,3,6-triphosphafulvene D (Mes* = 2,4,6-t-Bu 3 C 6 H 2 ) 12 successfully trapped HF and afforded a heterocyclic compound bearing the exo P(H)-ylide moiety. 13 The considerably polarized canonical structure D′ would induce regioselective hydrofluorination, and the aromaticity of the resultant five-membered ring would facilitate construction of the P-ylide bearing a P−H bond.…”

Section: ■ Introductionmentioning

confidence: 99%

“…We speculated that the use of phosphorus compounds would provide an alternative approach for the efficient capture of HF, principally because of the large P–F bond energy (119.4 kcal mol –1 ) . The kinetically stabilized 1,3,6-triphosphafulvene D (Mes* = 2,4,6- t -Bu 3 C 6 H 2 ) successfully trapped HF and afforded a heterocyclic compound bearing the exo P(H)-ylide moiety .…”

Section: Introductionmentioning

confidence: 99%

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Chemical Detection of Hydrogen Fluoride by the Phosphorus Congener of Cyclobutane-1,3-diyl

2015

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Heteroaryl-substituted air-tolerant 2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyls in the open-shell singlet state were synthesized by a sterically promoted regioselective S(N)Ar process. Here we demonstrate that these diyls are effective for capturing hydrogen fluoride (HF) generated by intermediary base-coordinated HF and amine-stabilized HF reagents. The hydrofluorination reaction predominantly occurred on the λ(3)σ(3)-phosphorus atoms to afford the energetically disfavored 1λ(5),3λ(5)-diphosphete. The positively charged t-butyl-substituted phosphorus atom trapped the fluoride anion, and the subsequent protonation was controlled by the steric effect. X-ray crystallographic analysis and an Atoms in Molecule study of the air-stable 1λ(5),3λ(5)-diphosphete bearing P-H and P-F bonds revealed that the delocalized ylidic linkages in the four-membered ring were almost identical, in contrast to the nonsymmetrically substituted 2,4-bis(2,4,6-tri-t-butylphenyl)-1,3-diphosphacyclobutane-2,4-diyl. Hydrofluorination efficiently induced a remarkable exchange of visible photoabsorption. The charge-transfer-type transition from highest occupied molecular orbital to lowest unoccupied molecular orbital was highly tuned, which is advantageous for the facile identification of HF. In contrast to hitherto known trapping reagents for HF based on cleavage of the H-F bond, several hydrofluorinated P-heterocycles were reconverted into the 1,3-diphosphacyclobutane-2,4-diyl by treatment with sodium hydride. However, in the hydrofluorination of the benzoyl-substituted 1,3-diphosphacyclobutane-2,4-diyl, fluorination and protonation occurred at the t-butyl-substituted phosphorus atom and the skeletal carbon atom, respectively, and the energetically preferable 1λ(5),3λ(3)-dihydrodiphosphete was isolated as a purple-blue crystalline compound. These findings are promising not only for the practical detection of HF but also for the development of fluorine technology based on the chemistry of phosphorus heterocycles.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%