Synthesis of 1,1′‐bisphosphinoferrocenes using electrophilic addition reactions of tungsten coordinated phosphenium ions and phosphine triflates

Bumraiwha, Hamdi F.; Sterenberg, Brian T.

doi:10.1016/j.jorganchem.2022.122511

Cited by 2 publications

(1 citation statement)

References 53 publications

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“…Unlike those, pnictogenium ions are also strong electrophiles, which can be attributed to the positive charge that attracts any nucleophile present. Consequently, the vast majority of phosphenium ions, [R 2 P] + , [2–33] arsenium ions, [R 2 As] + , [34–51] stibenium ions, [R 2 Sb] +[52–59] and bismuthenium ions, [R 2 Bi] + , [60–72] reported in the literature are either affected by ion pairing or stabilized by electron‐rich ligands or substituents, which inter‐ or intramolecularly fill the vacant p‐orbital. These electronically stabilized pnictogenium ions often have a dramatically reduced Lewis acidity and cannot be regarded as genuine 6 VE species as they fulfill or even exceed the octet rule.…”

Section: Introductionmentioning

confidence: 99%

Kinetically Stabilized Diarylpnictogenium Ions

2023

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The newly prepared and fully characterized stibenium and bismuthenium ions [RindMesE]+ (E=Sb, Bi; Rind=dispiro[fluorene‐9,3′‐(1′,1′,7′,7′‐tetramethyl‐s‐hydrindacen‐4′‐yl)‐5′,9′′‐fluorene) were rigorously compared to the previously communicated phosphenium and arsenium ions (E=P, As) as well as the bis(m‐terphenyl) pnictogenium ions [(2,6‐Mes2C6H3)2E]+ (E=Sb, Bi). It is demonstrated that the choice of the aryl substituents dramatically effects the molecular structures (e. g. the primary E−C bond lengths) and the electronic structures (e. g. the energy of the LUMOs).

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Section: Introductionmentioning

confidence: 99%

Kinetically Stabilized Diarylpnictogenium Ions

2023

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Exploring Electrophilic Hydrophosphination via Metal Phosphenium Intermediates

Belli,

Muir,

Dyck

et al. 2024

Chemistry A European J

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Two Mo(0) phosphenium complexes containing ancillary secondary phosphine ligands have been investigated with respect to their ability to participate in electrophilic addition at unsaturated substrates and subsequent P‐H hydride transfer to “quench” the resulting carbocations. These studies provide stoichiometric “proof of concept” for a proposed new metal‐catalyzed electrophilic hydrophosphination mechanism. The more strongly Lewis acidic phosphenium complex, [Mo(CO)4(PR2H)(PR2)]+ (R = Ph, Tolp), cleanly hydrophosphinates 1,1‐diphenylethylene, benzophenone, and ethylene, while other substrates react rapidly to give products resulting from competing electrophilic processes. A less Lewis acidic complex, [Mo(CO)3(PR2H)2(PR2)]+, generally reacts more slowly but participates in clean hydrophosphination of a wider range of unsaturated substrates, including styrene, indene, 1‐hexene, and cyclohexanone, in addition to 1,1‐diphenylethylene, benzophenone, and ethylene. Mechanistic studies are described, including stoichiometric control reactions and computational and kinetic analyses, which probe whether the observed P‐H addition actually does occur by the proposed electrophilic mechanism, and whether hydridic P‐H transfer in this system is intra‐ or intermolecular. Preliminary reactivity studies indicate challenges that must be addressed to exploit these promising results in catalysis.

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Synthesis of 1,1′‐bisphosphinoferrocenes using electrophilic addition reactions of tungsten coordinated phosphenium ions and phosphine triflates

Cited by 2 publications

References 53 publications

Kinetically Stabilized Diarylpnictogenium Ions

Kinetically Stabilized Diarylpnictogenium Ions

Exploring Electrophilic Hydrophosphination via Metal Phosphenium Intermediates

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