Sterically constrained tricyclic phosphine: redox behaviour, reductive and oxidative cleavage of P–C bonds, generation of a dilithium phosphaindole as a promising synthon in phosphine chemistry

Brand, Alexander S.; Schulz, Stephen; Hepp, Alexander; Weigand, Jan J.; Uhl, Werner

doi:10.1039/d0sc06155g

Cited by 3 publications

(2 citation statements)

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“…This means that similarly to [ 1 + ][PF 6 ], [ 1 + ][Cl] is probably a separated ion pair in solution. Noteworthy, in 2018, Uhl reported the synthesis of a neutral geometrically constrained phosphine in CCC pincer-type ligand that exhibited unusual reactivity in coordination chemistry and synthesis of new heterocyclic molecules …”

Section: Resultsmentioning

confidence: 99%

“…Noteworthy, in 2018, Uhl reported the synthesis of a neutral geometrically constrained phosphine in CCC pincertype ligand that exhibited unusual reactivity in coordination chemistry 19 and synthesis of new heterocyclic molecules. 20 The geometry around P1 in 1 + is significantly distorted from the trigonal pyramidal geometry of the analogous, not geometrically constrained carbodiphosphorane-PPh 2 adduct [(Ph 3 P) 2 C−PPh 2 ] + that adopts a local C 3v symmetry. 21 The rigid, tridentate carbodiphosphorane-based ligand enforces a strained geometry around the P1 center in 1 + with a significant distortion along the P1−C1 axis, resulting in a local C s symmetry.…”

Section: ■ Introductionmentioning

confidence: 96%

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Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar–F Bonds

et al. 2023

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The synthesis, isolation, and reactivity of a cationic, geometrically constrained σ 3 -P compound in the hexaphenylcarbodiphosphoranyl-based pincer-type ligand (1 + ) are reported. 1 + reacts with electron-poor fluoroarenes via an oxidative additiontype reaction of the C−F bond to the P III -center, yielding new fluorophosphorane-type species (P V ). This reactivity of 1 + was used in the catalytic hydrodefluorination of Ar−F bonds with PhSiH 3 , and in a catalytic C−N bond-forming cross-coupling reactions between fluoroarenes and aminosilanes. Importantly, 1 + in these catalytic reactions closely mimics the mode of action of the transition metal-based catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 96%

Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar–F Bonds

et al. 2023

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A Benzodiphosphaborolediide

Pearce

Canham

Nixon

et al. 2021

Chemistry A European J

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The first example of a diphosphaborolediide, the benzo‐fused [C6H4P2BPh]2− (12−), is prepared from ortho‐bis(phosphino)benzene (C6H4{PH2}) and dichlorophenylborane, via a sequential lithiation approach. The dilithio‐salt can be obtained as an oligomeric THF solvate or discrete TMEDA adduct, both of which are fully characterized, including by X‐ray diffraction. Alongside NICS calculations, data strongly suggest some aromaticity within 12−, which is further supported by preliminary coordination studies that demonstrate η5‐coordination to a zerovalent molybdenum center, as observed crystallographically for the oligomeric [{Mo(CO)3(η5‐1)}{μ‐η1‐Mo(CO)3(TMEDA)}2] ⋅ [μ‐Li(THF)][μ‐Li(TMEDA)].

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Geometrically Deformed and Conformationally Rigid Phosphorus Trisamides Featuring an Unsymmetrical Backbone

Beims,

Greven,

Schmidtmann

et al. 2023

Chemistry A European J

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Nonclassical P(III) centers have attracted much attention in recent years. Incorporating a P(III) center in a rigid bicyclic platform offers a particularly attractive way to invoke significant geometric distortion of the phosphorus atom that may in turn induce unusual reactivity. Although still relatively scarcely explored, phosphorus centers enforced in a non‐C3 symmetry have gained significant traction lately. However, the current scaffolds are based on a relatively limited set of design principles and ligand platforms associated therewith. We herein focus on the synthesis as well as versatile oxidation, addition and coordination chemistry of geometrically distorted P(III) species featuring a synthetically modular, nonsymmetric trisamine platform derived from 2‐(methylamino)‐N‐(2‐(methylamino)phenyl)benzenesulfonamide.

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Sterically constrained tricyclic phosphine: redox behaviour, reductive and oxidative cleavage of P–C bonds, generation of a dilithium phosphaindole as a promising synthon in phosphine chemistry

Abstract: The redox behavior of sterically constrained tricyclic phosphine 3a was investigated by spectroelectrochemistry. The data suggested a highly negative reduction potential with the reversible formation of a dianionic species. Accordingly,...

Cited by 3 publications

References 115 publications

Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar–F Bonds

Metallomimetic Chemistry of a Cationic, Geometrically Constrained Phosphine in the Catalytic Hydrodefluorination and Amination of Ar–F Bonds

A Benzodiphosphaborolediide

Geometrically Deformed and Conformationally Rigid Phosphorus Trisamides Featuring an Unsymmetrical Backbone

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