Structures and heats of formation of the neutral and ionic PNO, NOP, and NPO systems from electronic structure calculations

Grant, Daniel J.; Dixon, David A.; Kemeny, A.; Francisco, Joseph S.

doi:10.1063/1.2902983

Cited by 19 publications

(34 citation statements)

References 47 publications

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“…Therefore, OPN is more reactive than N 2 O, as indicated by its reversible coupling reaction with CO, as nitrenes and heavier phosphinidenes do. Given the very recently discovered reactions of nitrenes and phosphinidenes with other small molecules such as O 2 , H 2 , and H 2 O, their reactions with OPN, as a potent interstellar species, should be of great interest, which are currently under investigations.…”

Section: Methodsmentioning

confidence: 99%

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Song

Liu

et al. 2018

Chemistry A European J

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Cyclic PON, a first 16-electron triatomic ring consisting of two first-row elements, has been generated through 193 nm laser photolysis of OPN in cryogenic matrices. When the photolysis (365 nm) was performed in the presence of CO, OPN combines CO and furnishes an exotic acyclic molecule OPNCO. Upon the 193 nm laser irradiation, OPNCO dissociates mainly to OPN and CO with traces of PN and CO . The identification of cyclic PON and OPNCO with IR spectroscopy is supported by N-labeling experiments and quantum chemical calculations.

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Section: Methodsmentioning

confidence: 99%

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Song

Liu

et al. 2018

Chemistry A European J

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“…The FMOs of the two linear isomers are similar to those of the corresponding PNO isomers. [26] Replacement of O by S alters the HOMOs by a large contribution from the sulfur p orbital. For the cyclic isomer, the HOMO is a combination of the out-of-plane PÀN bonding p-orbital with nonbonding to the sulfur p orbital, and the LUMO is simply the p*(PÀN) orbital.…”

Section: Methodsmentioning

confidence: 99%

Experimental Observation of the 16‐Electron Molecules SPN, SNP, and Cyclic PSN

et al. 2012

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Dreiatomiger Ring mit 16 Elektronen: Thiazylidinphosphan (SNP) wurde erstmals hergestellt, und zwar durch Blitzvakuumpyrolyse (ca. 1000 °C) oder Laserphotolyse (193 nm) von SP(N3)3. In der Ar‐Matrix bei 16 K tritt Photoisomerisierung von SNP zu cyclischem Thiazaphosphirin (cyc‐PSN) und Thiophosphorylnitrid (SPN) auf. cyc‐PSN ist das erste experimentell beobachtete cyclische dreiatomige Molekül mit 16 Elektronen.

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“…Only one recent ab initio quantum chemical study came to the conclusion that the OPN isomer is slightly more stable. [18] Hence the PNO story shows how difficult it can be to calculate such seemingly simple triatomic molecules, and also provides a textbook example for the fruitful interaction between experimental and theoretical studies. Willner and co-workers entitled their contribution "Elusive O = P N, a rare example of phosphorus s 2 l 5 coordination."…”

Section: ! Onp ð1þmentioning

confidence: 99%

OPN and SPN: Small Molecules with Great Potential

Himmel

Linti

2012

Angew Chem Int Ed

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electronic structure · matrix isolation · phosphorus · quantum chemistry · reactive intermediates Matrix isolation is now a well-established method for the characterization of highly reactive species and reaction intermediates. [1] Most importantly, it paves the way for later work on a preparative scale. Willner and co-workers very recently reported on the preparation of the molecule OPN [2] in an inert-gas matrix by photolysis of the precursor compound OP(N 3 ) 3 . [3] OPN could be photoisomerized rever-To appreciate the scientific merit of this work, one should first consider the special importance of PO and PN bonds in chemistry. The P = O bond with a tetracoordinated phosphorus atom, which is best formulated not as a double bond but as a single bond with charges on the phosphorus and oxygen atoms, is of key importance in biomolecules such as ATP and DNA. Its stability can be used in a large variety of applications, such as the Wittig reaction. The two-atom molecule PO was isolated in matrix experiments by photolysis of P 4 /O 2 mixtures. [4] The P = N bond with a tetracoordinated phosphorus atom, again best formulated as a polar single bond, is also of significant interest, and could be found for example, in cyclophosphazenes and polyposphazenes. The molecule PN, detected already very early in the gas phase, [5] was later isolated in inert-gas matrices. [6] In the solid state phosphorus mononitride PN is an oligomer of unknown structure. [7] Recently, a carbene-stabilized phosphorus mononitride was synthesized which proved to be stable at room temperature (see Scheme 1). [8] However, the PÀN bond length of 170.85 pm argues for a single bond. It is part of a series of remarkable N-heterocyclic carbene(NHC)-stabilized potentially multiply bonded species like P 2 (NHC) 2 . [9] Moreover, the isoelectronic anion CP À was isolated both as ligand in a transition-metal complex and also bound to the Lewis acid B(CF 3 ) 3 (see Scheme 2). [10] The neutral RCP compounds, first prepared by Becker and et al. (with R = tBu), were shown to exhibit a rich chemistry. [11] OPN is isoelectronic to SiO 2 , [12] and indeed a solid material of the composition OPN could be synthesized in both a b-cristobalite and an amorphous form (which was slightly less stable thermodynamically) by the reaction of urea or melamine with a phosphorus precursor. [13] Hence one expects that OPN will display interesting reactivity.The story of the isolation of this molecule started with a matrix and quantum chemical study by Schnçckel, Ahlrichs, and Schunk in 1988. [14] In the introduction of their article the authors stated "We now wanted to clarify whether P V can also occur in compounds with coordination number two". The molecule was formed by matrix photolysis of a PN/O 3 mixture. Surprisingly, the IR data clearly indicated formation of PNO rather than its isomer OPN. Hence, as the authors stated, "the structure of PNO contradicts chemical intuition, according to which the most electropositive atom should assume the central position in a triatomi...

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Structures and heats of formation of the neutral and ionic PNO, NOP, and NPO systems from electronic structure calculations

Cited by 19 publications

References 47 publications

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Photochemistry of OPN: Formation of Cyclic PON and Reversible Combination with Carbon Monoxide

Experimental Observation of the 16‐Electron Molecules SPN, SNP, and Cyclic PSN

OPN and SPN: Small Molecules with Great Potential

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