Group 13–Group 15 Element Bonds Replacing Carbon–Carbon Bonds in Main Group Polyolefin Analogs

Staubitz, Anne; Hoffmann, Jonas; Gliese, Philipp J.

doi:10.1002/9783527819140.ch2_1

Cited by 6 publications

(10 citation statements)

References 48 publications

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“…Kugelrohr distillation was performed with a Büchi B-585 Kugelrohr oven (Büchi, Flawil, Switzerland). All NMR -spectra were carried out at 23 C. 1 H NMR (601 MHz) and 13 C{ 1 H} NMR (151 MHz) spectra were recorded on a Bruker Avance Neo spectrometer equipped with a TXI probe head. 1 H NMR (601 MHz), 13 C{ 1 H} NMR (151 MHz), 11 B{ 1 H} NMR (193 MHz), 29 Si{ 1 H} NMR (119 MHz), 31 P{ 1 H} NMR (243 MHz), 119 Sn{ 1 H} NMR (223 MHz) spectra were recorded on a Bruker Avance Neo spectrometer equipped with a BBO probe head.…”

Section: Methodsmentioning

confidence: 99%

“…All NMR -spectra were carried out at 23 C. 1 H NMR (601 MHz) and 13 C{ 1 H} NMR (151 MHz) spectra were recorded on a Bruker Avance Neo spectrometer equipped with a TXI probe head. 1 H NMR (601 MHz), 13 C{ 1 H} NMR (151 MHz), 11 B{ 1 H} NMR (193 MHz), 29 Si{ 1 H} NMR (119 MHz), 31 P{ 1 H} NMR (243 MHz), 119 Sn{ 1 H} NMR (223 MHz) spectra were recorded on a Bruker Avance Neo spectrometer equipped with a BBO probe head. 1 H, 13 C, 29 Si, 31 P NMR, 119 Sn NMR spectra are reported on the δ scale (ppm) and are referenced against tetramethylsilane respectively Where possible, NMR signals were assigned using 1 H COSY, 1 H/ 1 H NOESY, 1 H/ 13 C HSQC and 1 H/ 13 C HMBC experiments.…”

Section: Methodsmentioning

confidence: 99%

“…After 1 h of stirring at 25 • C, the solvent was removed, and the reaction mixture was dissolved in n-hexane (10 mL) at 60 • C. This solution was transferred through syringe filters into another Schlenk flask and stored in a freezer (−30 • C) in the glove box to obtain colorless crystals (F, 44 mg, 0.125 mmol, 94%). 1 H NMR (601 MHz, C 6 D 6 ): δ = 7.89 (dd, 3 J = 12.8, 7.6 Hz, 2H, H-3), 7.12-6.98 (m, 10H, H-4,5 and H-9,10,11), 6.95 (dd, 3 J = 7.6, 4 J = 3.3 Hz, 2H, H-6), 6.84 (s (br), 4H, H-8,12), 6.30 (dq, 1 J P-H = 396.4 Hz, 2 J PH-BH3 = 6.7 Hz, 1H, PH), 2.13 (d, 1 J BH = 126.9 Hz, 3H, BH 3 ) ppm. Lithium bis(biphenyl-2-yl)phosphide (E) In the glove box, phosphine D (20.0 mg, 59.7 µmol) was dissolved in benzene (10 mL) and n-butyllithium (0.50 mL, 125 µmol, 2.5 M in hexanes) was added at 25 • C. The reaction mixture was stirred for 2 h and the supernatant was filtered through syringe filters.…”

Section: Methodsmentioning

confidence: 99%

“…Their use in catalysis is therefore undisputed. These fragments also occur in inorganic polymers and rings [1][2][3]. The most common ones among these are trivalent diarylphosphines, Ar 2 PH, the corresponding tetravalent phosphine boranes, R 2 PH-BH 3 , the corresponding lithiated species, Ar 2 PLi, and the aminospecies Ar 2 PNR 2 .…”

Section: Introductionmentioning

confidence: 99%

“…As described above diarylphosphides are prepared from reductive C-P bond cleavage of a triaryl phosphine, by reduction of a diarylchlorophosphine with a hydride-based reductant (e.g., LAH) or deprotonation of diarylphosphines with butyllithium (BuLi). They represent precursors for prominent ligands such as 1,2-bis(diphenylphosphino)methane (dppm) 1,2-bis(diphenylphosphino)ethane (dppe) [1]. Moreover, diarylphosphides can also serve as reagents.…”

Section: Introductionmentioning

confidence: 99%

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The bis(Biphenyl)phosphorus Fragment in Trivalent and Tetravalent P-Environments

et al. 2021

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Diaryl substituted phosphorus (III) compounds are commonly used motifs in synthesis. Although the basic synthetic routes to these molecules starting from PCl3 are well reported, sterically hindered aryl substituents can be difficult to introduce, especially if the P atom is in ortho position to another group. This work explores the chemistry of the bis(biphenyl)phosphorus(III) fragment. As third substituents, H, M, Cl, NR2, two group 14 element substituents and also Li were introduced in high-yielding processes offering a wide chemical variety of the bis(biphenyl) phosphine motif. In addition, also a tetravalent phosphine borane adduct was isolated. All structures were thoroughly investigated by heteronuclear NMR spectroscopic analysis. Furthermore, the reaction conditions are discussed in connection with the structures and four crystal structures of the aminophosphine, phosphine, phosphine borane and phosphide are provided. The latter crystallized as a dimer with a unique planar P2Li2 ring, which is stabilized by the non-covalent C⋯Li interaction arising from the biphenyl motif and represents a rare example of a donor-free planar P2Li2 ring.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The bis(Biphenyl)phosphorus Fragment in Trivalent and Tetravalent P-Environments

et al. 2021

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Phosphorus‐Boron Multiple Bonding in the π Radical HBP

Wang

Jiang

Wang

et al. 2023

Chemistry A European J

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The HBP radical was generated via the reaction of laser ablated boron atom with PH3 in a solid neon matrix, which is identified via IR spectroscopy with isotopic substitutions and quantum chemical calculations. The results show that HBP has a 2Π electronic ground state with a short B−P bond. Bonding analysis indicates that besides an electron‐sharing σ bond, there are two degenerate π bonding orbitals that are occupied by three electrons, resulting in a bond order of two and half between P and B. This is in sharp contrast to the bonding properties of the isovalent HNB, which was characterized to be a N≡B triply bonded σ radical with the unpaired electron locating on the B atom.

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Changing up BN-Polystyrene: Effect of Substitution Pattern on the Free-Radical Polymerization and Polymer Properties

et al. 2019

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Azaborinine-substituted polymers are poised to dramatically expand the diversity and functionality of polystyrenes via BN for CC substitution, but this new class of materials remains underexplored. Although formally isosteric to the respective all-carbon polystyrene derivatives, polarization due to the difference in electronegativity between B and N can have a distinct effect on polymerizability and the resulting polymer properties. Discussed herein is the successful preparation of a series of new isomeric azaborinine-substituted polymers via standard free-radical polymerization. We investigate the effects of the substitution pattern of vinylated B-mesityl azaborinines, that is, the position of the vinyl group relative to the BN moiety, on the polymerization reactivity and physical properties of the respective polymers. Copolymerization experiments with the parent styrene, as well as meta-and para-mesitylstyrene as direct all-carbon analogues of the azaborinine monomers, reveal that depending on the substitution pattern the more polarized azaborinines are incorporated to a lesser (B-Mes in para-position) or larger extent (B-Mes in meta-position) than the all-carbon analogues. Computational studies offer insights into the subtle electronic effects that result in this differential reactivity. We also compare the polymer properties to those of the all-carbon polystyrene analogues.

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Group 13–Group 15 Element Bonds Replacing Carbon–Carbon Bonds in Main Group Polyolefin Analogs

Cited by 6 publications

References 48 publications

The bis(Biphenyl)phosphorus Fragment in Trivalent and Tetravalent P-Environments

The bis(Biphenyl)phosphorus Fragment in Trivalent and Tetravalent P-Environments

Phosphorus‐Boron Multiple Bonding in the π Radical HBP

Changing up BN-Polystyrene: Effect of Substitution Pattern on the Free-Radical Polymerization and Polymer Properties

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