Dominance of unique P⋯π phosphorus bonding with π donors: evidence using matrix isolation infrared spectroscopy and computational methodology

Chandra, Swaroop; Suryaprasad, B.; Ramanathan, N.; Sundararajan, K.

doi:10.1039/d0cp02880k

Cited by 14 publications

(11 citation statements)

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“…Phosphorus is known to exist at two stable oxidation states: trivalent (+3) and pentavalent (+5). Phosphorus bonding at both these states has been observed quite recurrently in experiments performed at our laboratory − and also in the extensive computational forays by several groups around the world, over the past decade. Phosphoryl chloride (POCl 3 ), a well-known precursor in the synthesis of organic phosphates, has proven to be an efficient prototype for the study of pentavalent phosphorus bonding.…”

Section: Introductionmentioning

confidence: 83%

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl₃-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

et al. 2022

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Both tetrel and pnicogen bonds are known to be induced through σ-/π-holes. This work reports computational and experimental evidence of the carbonyl carbon of acetone hosting a tetrel bond by dispersion rather electrostatic forces, for the first time, while phosphorus of POCl 3 sustains pnicogen bonding via the σ-hole. Heterodimers of POCl 3 with acetone (CH 3 COCH 3 ) have been isolated within inert gas matrixes of Ar and N 2 at 12 K. Characteristic vibrational bands at P�O stretching of POCl 3 and C�O stretching of CH 3 COCH 3 have been obtained in support of the computations. The potential energy surface has been traced computationally using ab initio and density functional methods. CH 3 COCH 3 harboring such a tetrel bond, in itself, is quite intriguing. The interplay of these interactions has been comprehended by the quantum theory of atoms in molecules, natural bond orbital, energy decomposition, electrostatic potential mapping, and noncovalent interaction analyses.

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Section: Introductionmentioning

confidence: 83%

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl₃-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

et al. 2022

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“…Isolated chemical systems could serve as examples of phosphorus bonding. Chandra and coworkers [ 97 ], and others [ 98 ], have reported such chemical systems expounded from studies of isolated entities. They showed that phosphorus can serve as an acceptor of electron density from the π electron cloud in partner molecules.…”

Section: Illustrative Crystalline Systemsmentioning

confidence: 99%

The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

2022

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The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.

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“…It has been observed in a varied set of crystals [ 11 , 12 , 13 , 14 , 15 , 16 ], and in the gas phase [ 17 ]. Experimental observations have been made in matrices [ 18 , 19 , 20 , 21 ] and via NMR measurements [ 22 , 23 ], and there are some experimental estimates of PnB energies [ 24 ] available. PnBs are involved in numerous chemical functions such as the capture and transport of halides across a phospholipid membrane [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models

2022

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Bonding within the AsF3 crystal is analyzed via quantum chemical methods so as to identify and quantify the pnicogen bonds that are present. The structure of a finite crystal segment containing nine molecules is compared with that of a fully optimized cluster of the same size. The geometries are qualitatively different, with a much larger binding energy within the optimized nonamer. Although the total interaction energy of a central unit with the remaining peripheral molecules is comparable for the two structures, the binding of the peripherals with one another is far larger in the optimized cluster. This distinction of much stronger total binding within the optimized cluster is not limited to the nonamer but repeats itself for smaller aggregates as well. The average binding energy of the cluster rises quickly with size, asymptotically approaching a value nearly triple that of the dimer.

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Dominance of unique P⋯π phosphorus bonding with π donors: evidence using matrix isolation infrared spectroscopy and computational methodology

Abstract: Albeit the first account of hypervalent…π interactions has been reported with halogen…π interactions, the feasibility of their extension to other hypervalent atoms as possible Lewis acids, is still open. In...

Cited by 14 publications

References 159 publications

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl₃-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl₃-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models

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Dominance of unique P⋯π phosphorus bonding with π donors: evidence using matrix isolation infrared spectroscopy and computational methodology

Abstract: Albeit the first account of hypervalent…π interactions has been reported with halogen…π interactions, the feasibility of their extension to other hypervalent atoms as possible Lewis acids, is still open. In...

Cited by 14 publications

References 159 publications

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl3-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl3-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

Involvement of Arsenic Atom of AsF3 in Five Pnicogen Bonds: Differences between X-ray Structure and Theoretical Models

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Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl₃-Acetone Heterodimer: Experimental Confirmation at Low Temperatures

Unique Dispersion-Induced Tetrel Bond with Co-operative σ-hole-Induced Pnicogen Bond in the POCl₃-Acetone Heterodimer: Experimental Confirmation at Low Temperatures