Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H2PEH2]n Oligomers (E=B, Al; n=1–15)

Pomogaeva, Anna V.; Scheer, Manfred; Timoshkin, Alexey Y.

doi:10.1002/chem.201803008

Cited by 8 publications

(3 citation statements)

References 78 publications

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“…This data suggests that as phosphinoborane chain grows, residual unreacted base can coordinate at the Lewis acidic boron terminus. The ability of Lewis bases to coordinate to oligomers formed in situ is consistent with recent computational studies by Pomogaeva, Timoshkin, and Scheer on phosphinoborane linear oligomer, [PH 2 ‐BH 2 ] 7 , where it was shown that the lowest unoccupied molecular orbital is localized at the boron terminus [40] . A further report on the stability of Lewis acid‐ and Lewis base adducts of analogous phosphinoborane decamers, [PH 2 ‐BH 2 ] 10 , showed that tethering of N‐heterocyclic carbenes (NHCs) to boron favors the formation of linear over cyclic species [41] .…”

Section: Resultssupporting

confidence: 88%

“…The ability of Lewis bases to coordinate to oligomers formed in situ is consistent with recent computational studies by Pomogaeva, Timoshkin, and Scheer on phosphinoborane linear oligomer, [PH 2 -BH 2 ] 7 , where it was shown that the lowest unoccupied molecular orbital is localized at the boron terminus. [40] A further report on the stability of Lewis acid-and Lewis base adducts of analogous phosphinoborane decamers, [PH 2 -BH 2 ] 10 , showed that tethering of N-heterocyclic carbenes (NHCs) to boron favors the formation of linear over cyclic species. [41] In contrast, the work also indicated that coordination of weaker Lewis bases (such as NH 3 ) at the boron terminus did not result in linear chains that were more stable than cyclic analogues.…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

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Transition‐Metal‐Free Dehydropolymerization of Phosphine–Boranes at Ambient Temperature

Wiebe

Kundu

LaPierre

et al. 2022

Chemistry A European J

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Stoichiometric reaction of phosphine–borane adducts RR'PH⋅BH3 (R=Ph, R’=H, Ph, Et, and R=R’=tBu) with the strong acid HNTf2 (Tf=SO2CF3) leads to H2 elimination and the formation of the triflimido derivatives, RR'PH⋅BH2(NTf2). Subsequent deprotonation by using bases, such as diisopropylethylamine or the carbene IPr (IPr=N,N’‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene), led to the formation of P‐mono‐ or ‐disubstituted polyphosphinoboranes [RR'P‐BH2]n. Evidence for the intermediacy of transient phosphinoborane monomers, RR'PBH2, was provided by trapping reactions.

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Section: Resultssupporting

confidence: 88%

Section: Chemistry-a European Journalmentioning

confidence: 99%

Transition‐Metal‐Free Dehydropolymerization of Phosphine–Boranes at Ambient Temperature

Wiebe

Kundu

LaPierre

et al. 2022

Chemistry A European J

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“…et al furnished a comprehensive account of how to transport the orbital occupation computation outcomes from Gaussian 16 software into the wave function analysis tool Multiwfn, in order to acquire discrete orbital occupation data at varying energy levels. Upon broadening with a Gaussian function, a continuous density of states (DOS) map can be generated [52].…”

Section: The Changes In the Orbital Occupation Of Each System Before ...mentioning

confidence: 99%

A DFT Study on Adsorption of SF6 Decomposition Products on Zr-MOF-808

Lei

Jiang

2023

Chemosensors

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Identifying the main byproducts of SF6 decomposition proves to be an effective strategy for determining the nature and severity of internal discharge faults in gas-insulated switchgears (GISs). In this research, it was suggested to utilize the coordination polymer Zr-MOF-808 as a sensor for the main byproducts of SF6 decomposition. This study examined the adsorption of SF6 and its main decomposition products (CF4, CS2, SO2, SO2F2, and SOF2) on Zr-MOF-808, utilizing Gaussian16 simulation software through a method anchored on quantum chemistry. Adsorption parameters were calculated and analyzed, including binding energy, charge transfer, adsorption distance, along with variations in bond length, bond angle, density of states, and frontier orbital of gas molecules. Our research indicated that the Zr-MOF-808 cluster demonstrated varying degrees of chemical adsorption for the six gases, leading to differential conductivity changes in each system following adsorption. Consequently, the detection of resistance value alterations in the materials would allow for the identification of the gas products.

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Organophosphorus Polymers

Green

Orthaber

2019

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This article discusses polymers containing phosphorus centers that impart essential properties, functions, and responses to the discussed materials. By incorporating this heteroelement, the toolbox for tailoring optical, electronic, and structural properties as well as chemical reactivity is greatly expanded over “carbon” analogs. We discuss unsaturated (e.g., phosphaalkenes), saturated (e.g., phosphine oxides), and cyclic (e.g., phospholes) phosphorus motifs incorporated into conjugated polymers. Such organophosphorus systems are believed to have a bright future in optoelectronic devices, with this being demonstrated in organic light‐emitting diodes as acceptor and emitter materials, and in fundamental studies as responsive sensor systems. Saturated organophosphorus polymers allow for chemical transformations at the phosphorus centers by means of oxidation, metal (Lewis acid) coordination, quaternization, and so on. These modifications and transformations are used in sensing, scavenging, and catalytic systems. Moreover, in this article, we cover selected inorganic polymers, that is, polymers having exclusively inorganic skeletal atoms. These mainly include the polyphosphine and phosphinoborane classes of materials, for which recent fundamental studies have illustrated their potential as ceramic precursors. Polymerization methods are often similar to those applied in organic polymers, but a large variety of polymerizations have also been specifically developed for phosphorus and other pnictogens, and these have also been employed to synthesize these fascinating materials.

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Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H₂PEH₂]_n Oligomers (E=B, Al; n=1–15)

Cited by 8 publications

References 78 publications

Transition‐Metal‐Free Dehydropolymerization of Phosphine–Boranes at Ambient Temperature

Transition‐Metal‐Free Dehydropolymerization of Phosphine–Boranes at Ambient Temperature

A DFT Study on Adsorption of SF6 Decomposition Products on Zr-MOF-808

Organophosphorus Polymers

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