Phospholes

Ananthnag, Guddekoppa S.; Balakrishna, Maravanji S.

doi:10.1016/b978-0-12-409547-2.14912-1

Cited by 4 publications

(3 citation statements)

References 109 publications

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“…To meet these criteria, we have chosen the radicals 2 , 8 , 12 , and 21 for further studies. Indeed, all of these radicals have remarkable RSE values, and the precursors to these radicals, namely, phosphirenes, phospholes, − phosphinines , (phosphabenzenes), and phosphepins, can be synthesized using well-established and effective techniques.…”

Section: Resultsmentioning

confidence: 99%

Stability of Carbocyclic Phosphinyl Radicals: Effect of Ring Size, Delocalization, and Sterics

2022

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In this computational study, we report on the stability of cyclic phosphinyl radicals with an aim for a systematical assessment of stabilization effects. The radical stabilization energies (RSEs) were calculated using isodesmic reactions for a large number of carbocyclic radicals possessing different ring sizes and grades of unsaturation. In general, the RSE values range from −1.2 to −14.0 kcal·mol–1, and they show practically no correlation with the spin populations at the P-centers. The RSE values correlate with the reaction Gibbs free energies calculated for the dimerization of the studied simple radicals. Therefore, the more easily accessible RSE values offer a cost-effective estimation of global stability in a straightforward manner. To explore the effect of unsaturation on the RSE values, delocalization energies were determined using appropriate isodesmic reactions. Introducing unsaturations beside the P-center into the backbone of the rings leads to an additive increase in the magnitude of the delocalization energy (∼10, 20, and 30 kcal·mol–1, respectively, for radicals with one, two, and three CC bonds in the conjugation). Parallelly, the spin populations at the P-centers also dwindle gradually by ∼0.1 e in the same order, indicating that the lone electron delocalizes over the π-system. Radicals containing exocyclic CC π-bonds were also investigated, and all of these radicals have rather similar stabilities independently of the ring size, outlining the primary importance of the two exocyclic π-bonds in the conjugation. Among the radicals involved in our study, those with the best electronic stabilization are the unsaturated three-, five-, six-, and seven-membered rings containing the maximum number of conjugated vinyl fragments. The largest delocalization energy of 31.5 kcal·mol–1 and the lowest obtained spin population of 0.665 e were found for the fully unsaturated seven-membered radical (phosphepin derivative). Importantly, the electronic stabilization effects alone are insufficient for stabilizing the radicals in monomeric forms epitomized by the exothermic dimerization energies (−40 to −58 kcal·mol–1). Therefore, it is essential to apply sterically demanding bulky substituents on the α-C-atoms. Tweaking the steric congestion enabled us to propose radicals that are expected to be stable against dimerization and, consequently, may be realistic target species for synthetic investigations. The effects contributing to the stability of radicals having sterically encumbered substituents have also been explored.

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Section: Resultsmentioning

confidence: 99%

Stability of Carbocyclic Phosphinyl Radicals: Effect of Ring Size, Delocalization, and Sterics

2022

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“…[62] In this direction, Naka and Imoto utilized various kinds of diarsenic ligands (diars = dpae, dpap, dpab, cis-dpav, transdpav, dpapz, and dpaq) [63] for the synthesis of Au complexes of the type [Au 2 Cl 2 (diars)]. By following the elegant method for the preparation of arsenic nucleophile (Scheme 1; method b) the authors generated diphenylarsanyllithium (Ph 2 AsLi) from the reaction of hexaphenylhexaarsine (As 6 Ph 6 ) with phenyl lithium, which on further treatment with alkyl, vinyl, or aryl dichlorides afforded corresponding bidentate ligands (15)(16)(17)(18)(19)(20)(21)…”

Section: Au(i) Complexes Of Arsinesmentioning

confidence: 99%

“…[4][5][6] Phosphorus-based compounds have only recently drawn attention as optoelectronic materials, and as a result, significant progress has been achieved in the study of organophosphorus compounds over the past ten years. [7][8][9] Due to the diagonal relation of phosphorus with carbon, various families of phosphorus-based compounds, including phosphaalkenes, [10] iminophosphines, [11][12] diphosphenes, [10] phosphaalkynes, [13] phosphinines, [14] and phospholes, [15][16] have been developed. This has created new opportunities for the logical development of novel compounds made up of heavier main group elements.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

et al. 2023

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Recent success in the synthesis of π-conjugated heavier pnictogen (As, Sb, and Bi) compounds and their transition metal complexes has led to the current surge in interest that led to significant development in the field of photophysical and optoelectronic properties of heavier pnictogens and their transition metal complexes. The presence of heavier pnictogens (As, Sb and Bi) in the molecular skeleton promotes inter-system crossing (ISC) and reverse inter-system crossing (RISC), because of the heavy atom effect, via altering the intermolecular interactions and orbital energy levels. As a result, π-conjugated heavier pnictogen compounds such as arsines, dibenzoarsepins, arsinoquinoline, heterofluorene, benzo[b]heterole (heterole = arsole, bismole, and stibole) show unique optoelectronic properties such as narrow bandgap, low-energy absorption, and long-wavelength emission than lighter pnictogen-based compounds. This review focuses on recent advances in the synthesis and photophysical properties of heavier pnictogen compounds. The synthesis and photophysical properties of heavier pnictogens are discussed and elaborated.

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Synthesis, Structures, and Properties for P^III‐Doped Hetero‐Buckybowls and Their Phosphonium Salts

Feng,

Hua,

Shang

et al. 2024

Chemistry A European J

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Doping polycyclic aromatic hydrocarbons with heteroatoms enables manipulation of their electronic structures. Herein, the structures and properties of phosphorus (P) doped heterosumanenes (HSEs) are regulated by varying the valence states of P‐dopant. The phosphine sulfide (PV) and chalcogens (S, Se, Te) co‐doped HSEs (1–3) are reduced to trivalent phosphorus (PIII) doped analogues 4–6. Then, the PIII‐dopants on 4–6 are converted to phosphonium salts (R4P+), giving 7–9. The valence states of P‐dopant show great influence on molecular geometries and electronic structures. Taking P and S co‐doped HSEs as example, bowl‐depths increase in the order of 1 (PV) < 7 (R4P+) < 4 (PIII), and the HOMO energy levels and HOMO‐LUMO gaps increase to be 7 < 1 < 4. Consistent with the theoretical calculation, the first oxidation potentials decrease and the absorption/emission bands show blue shift from 7 to 1 to 4. The transformation of PV to PIII leads to large variations on the coordination with Ag+, owing to the alteration of coordination site from P=S to PIII. The phosphonium salts show ring‐opening of phosphole rings under electrochemical reduction. It is found that chalcogen atoms play pivotal roles on coordination patterns of coordination complexes and the conversion rates of ring‐opening reactions.

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Phospholes

Cited by 4 publications

References 109 publications

Stability of Carbocyclic Phosphinyl Radicals: Effect of Ring Size, Delocalization, and Sterics

Stability of Carbocyclic Phosphinyl Radicals: Effect of Ring Size, Delocalization, and Sterics

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

Synthesis, Structures, and Properties for P^III‐Doped Hetero‐Buckybowls and Their Phosphonium Salts

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Phospholes

Cited by 4 publications

References 109 publications

Stability of Carbocyclic Phosphinyl Radicals: Effect of Ring Size, Delocalization, and Sterics

Stability of Carbocyclic Phosphinyl Radicals: Effect of Ring Size, Delocalization, and Sterics

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

Synthesis, Structures, and Properties for PIII‐Doped Hetero‐Buckybowls and Their Phosphonium Salts

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Synthesis, Structures, and Properties for P^III‐Doped Hetero‐Buckybowls and Their Phosphonium Salts