P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

Taube, Clemens; Schwedtmann, Kai; Noikham, Medena; Somsook, Ekasith; Hennersdorf, Felix; Wolf, Robert; Weigand, Jan J.

doi:10.1002/ange.201911483

Cited by 6 publications

(2 citation statements)

References 75 publications

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“…R = Me, i Pr, t Bu, or Ph), a class of novel cationic ligands and further examples of pyrazolyl-substituted phosphanes with two reactive P–N bonds . We are particularly interested in such types of phosphanes as they can be used for the targeted synthesis of polyphosphanes via P–N/P–P-bond metathesis . Salts R 8 [OTf] are synthesized by the reaction of 2a Cl2 [OTf] with two equiv of the respective 3,5-alky/aryl-1-(trimethylsilyl)pyrazole in Et 2 O at room temperature .…”

Section: Resultssupporting

confidence: 85%

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts

et al. 2020

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A novel method for the one-pot synthesis of diannulated 1,4,2-diazaphospholium triflate salts by a Me3SiOTf-mediated self-condensation of dichlorophosphaneyl aza-(poly)cyclic aromatic hydrocarbons (aza-(P)AHs; namely, pyridine, quinoline, phenanthridine, and benzo[d]thiazole) is reported. The diannulated 1,4,2-diazaphospholium triflate salts are characterized by multinuclear NMR spectroscopy, X-ray analysis, as well as their calculated NICS values, underlining their aromatic character. Quantum mechanical calculations shed light on the intermolecular reaction mechanism. Follow up chemistry, such as the halogenation reaction with XeF2 or SO2Cl2 with the dipyridinium derivative selectively yields the respective dihalo-σ4,λ5- and tetrahalo-σ5,λ6-diazaphospholium triflate salts. The dihalo-σ4,λ5-diazaphospholium triflate salt serves well as a surrogate for the introduction of the cationic 2-(1,2′-bipyridin)-1-iumyl ligand (1,2′-bipyl), the monocationic structural isomer of the prototypical 2,2′-bipyridine ligand (2,2′-bipy).

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Section: Resultssupporting

confidence: 85%

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts

et al. 2020

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“…It is known that cyclophosphanes can undergo interconversion reactions in protic solvents to give thermodynamically more favored ring sizes . Therefore, we assume that triphosphirane 15 2+ undergoes a ring‐interconversion as a result of a P−P/P−P bond metathesis to form cations 17 3+ and 11 2+ (Scheme , II ) . We have been able to separate salt 17 [OTf] 3 from the reaction mixture in yields of 45 % by slow vapor diffusion of CH 2 Cl 2 into the reaction mixture at −30 °C.…”

Section: Resultsmentioning

confidence: 99%

Coordination Chemistry and Methylation of Mixed‐Substituted Tetraphosphetanes (RP−PtBu)₂ (R=Ph, Py)

Schoemaker

Kossatz

Schwedtmann

et al. 2020

Chemistry A European J

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Synthesis of mixed‐substituted tetraphosphetanes (RP−PtBu)2 (R=Ph (4), Py (5); Py=2‐pyridyl) is achieved from the condensation of dipyrazolylphosphanes RPpyr2 (R=Py (1), Ph (3); pyr=3,5‐dimethylpyrazolyl) as P1‐building block (R−P) and tBuPH2 in an equimolar ratio. Compound 5 is of special interest since the presence of two pyridyl‐substituents as well as the P4‐core allows for a rich coordination chemistry with coinage metal salts [Cu(MeCN)4][OTf], Ag[OTf] and in situ formed [Au(tht)][OTf] (tht=tetrahydrothiophene). Both tetraphosphetanes undergo alkylation reaction with MeOTf to give a series of tetraphosphetanium and tetraphosphetanediium triflate salts with additional methylation of the pyridyl‐moiety in case of 5 resulting in interesting novel cyclic trications. Harsh reaction condition and an excess of MeOTf converts 5 into the cyclic trication [‐P(MePy)PMe2P(MePy)PtBu‐]3+ (133+; MePy=1‐methylpyridiniumyl) through the elimination of isobutene. This salt undergoes a complicated rearrangement reaction involving a P−P/P−P bond metathesis to form trication [‐P(MePy)3PtBu‐]3+ (173+) when reacted with Me2PPMe2.

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Zwitterionic 2‐Phosphaethene‐thiolates [(L_C)P=CS(L_C/P)]⁺ as PCS Building Blocks (L_C=NHC, L_P=PR₃)

Royla,

Schwedtmann,

Gomila

et al. 2024

Angewandte Chemie

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The zwitterionic compounds [(LC)P=CS(LC/P)]+ (3+, LC = NHC, LP = PR3), featuring cationic substituents at the phosphorus and carbon atoms, are synthesized as their triflate salts at a multi‐gram scale from the reaction of Lewis base adducts of CS2, namely LC/P–CS2 (4), with a combination of [(LCP)4][OTf]4 (1[OTf]4) and Ph3P. The feasibility of using 3+ as PCS building blocks is showcased in their reactions with representative electrophiles (MeOTf) and nucleophiles (MesMgBr, Ph3PCH2), leading to selective functionalization of the PCS core at the S‐ and P‐terminus, respectively. Additionally, it is reported that 3+ can function as ambident nucleophiles with AgOTf (2 equivalents), affording unprecedented linear coordination polymer [Ag2(OTf)3‐μ2:κP,κS–((LC)P=CS(PCy3))]+ (6b), where the PCS moiety acts as a bridging ligand in transition metal complexes for the first time. Reduction of 3+ facilitates the cleavage of the P‐ and C‐bound substituents leading to the formation of the [PCS]– anion. Moreover, cycloaddition reactions of 3+ with 1[OTf]4 are shown to selectively yield five‐ and eight‐membered polyphosphorus heterocycles. Preliminary results suggest the possibility of activating the C–S bond in [(LC)P=CS(LC)]+, resulting in the formation of [(LC)P=C(LC)–P(LC)][OTf]2, 12[OTf]2, which may serve as a synthon for the PCP unit in future studies.

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P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

Cited by 6 publications

References 75 publications

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts

Coordination Chemistry and Methylation of Mixed‐Substituted Tetraphosphetanes (RP−PtBu)₂ (R=Ph, Py)

Zwitterionic 2‐Phosphaethene‐thiolates [(L_C)P=CS(L_C/P)]⁺ as PCS Building Blocks (L_C=NHC, L_P=PR₃)

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P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

Cited by 6 publications

References 75 publications

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts

Coordination Chemistry and Methylation of Mixed‐Substituted Tetraphosphetanes (RP−PtBu)2 (R=Ph, Py)

Zwitterionic 2‐Phosphaethene‐thiolates [(LC)P=CS(LC/P)]+ as PCS Building Blocks (LC=NHC, LP=PR3)

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Product

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About

Coordination Chemistry and Methylation of Mixed‐Substituted Tetraphosphetanes (RP−PtBu)₂ (R=Ph, Py)

Zwitterionic 2‐Phosphaethene‐thiolates [(L_C)P=CS(L_C/P)]⁺ as PCS Building Blocks (L_C=NHC, L_P=PR₃)