Selective and Reversible Fluoride Complexation from Water by a Cyclic Tri(phosphonio)methanide Dication

Yogendra, Sivathmeehan; Hennersdorf, Felix; Bauzá, Antonio; Frontera, Antonio; Fischer, Roland; Weigand, Jan J.

doi:10.1002/ange.201701570

Cited by 3 publications

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“…425 In addition the dication 543 underwent intramolecular C-H bond activation of a phenyl ring upon drastic conditions that cyclized into the unprecedented tri(phosphonio)methanide dication 550 in high yield. 427 The 31 P NMR of dication 550 reflected an AX 2 spin system which is consistent with the proposed structure. Definitive proof for the cyclization of 543 into 550 was provided by XRD analysis which showed the planarity of the bicyclic dication, having short P-C bond distances as a consequence of the negative hyperconjugation of the π lone pair at methanide C-atom across the σ*(P-C Ph ) orbitals.…”

supporting

confidence: 78%

“…The appropriate choice of Bronsted acid (HBF 4 ) permitted the selective protonation at the C ylide position of the CDP framework in moderate yield (Scheme 208). [422] [Cl] reacted with AlMe 3 to reach the methylsubstituted P,C,P-pincer complex [427][AlCl 2 Me 2 ] in excellent yield via ligand metathesis instead deprotonation of the ligand backbone that was observed upon addition of MeLi. Using LiHMDS, the selectivity completely switched toward deprotonation of the CH 2 moiety at the ligand backbone to give the neutral P,C,P-pincer platform 428.…”

Section: ) the Formation Of [256c]mentioning

confidence: 99%

“…Subsequent deprotonation step by the triflate drives the formation of the tri(phosphonio)methanide dication 550. 427 The dication 550 reacts with fluoride sources (either KF, AgF, or [NBu 4 ][F]) to yield the fluorinated cation 551 that is characterized in 31 P NMR by a AMUX spin system, with only two phosphorus nuclei correlating with the fluorine in 19 4 ] (3 equiv) produced the fluorinated cation 557a in minimal amounts that precluded its isolation. Improved yields (26% and 55%) were achieved by starting from the respective salts [554a][BAr Cl 4 ] or [555b]-[BAr Cl 4 ] and benzotrifluoride.…”

Section: Reactivity Of Double Ylides Toward Main Group Elementsmentioning

confidence: 99%

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Geminal Dianions Stabilized by Main Group Elements

2019

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This review is dedicated to the chemistry of stable and isolable species that bear two lone pairs at the same C center, i.e. geminal dianions, stabilized by main group elements. Three cases can thus be considered: the gem dilithio derivative, for which the two substituents at C are neutral, the ylidiide derivatives, for which one substituent is neutral while the other is charged, and finally the geminal bisylides, for which the two substituents are positively charged. In this review the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications. Reactivity of doubleylides towards organic compounds. 4.4. Coordination chemistry of double ylides to metallic species. 4.4.1. Coordination to Group 2 Metals. 4.4.2. Coordination to Actinides: Uranium Complexes 4.4.3. Coordination to Group 4 Metals: Zirconium Complexes 4.4.4. Coordination to Group 6 Metals: Tungsten Complexes 4.4.5. Coordination to Group 7 Metals: Manganese and Rhenium Complexes 4.4.6. Coordination to Group 8 Metals: Iron Complexes 4.4.7. Coordination to Group 9 Metals: Rhodium and Iridium Complexes 4.4.8. Coordination to Group 10 Metals 4.4.9. Coordination to Group 11 (Coinage) Metals 4.4.10. Coordination to Group 12 Metals 4.5. Reactivity of double ylides towards main group elements. 4.5.1. Group 13 4.5.2. Group 14 4.5.3. Group 15 4.5.4. Group 16 4.5.5. Group 17 4.6. Carbodicarbenes 4.6.1. Synthesis 4.6.2. Reactivity 4.6.3. Coordination chemistry 4.6.4. Reactivity with main group elements 5. Conclusion 6. Acknowledgements 7. References lengths in complexes [(7)Mg(THF)] 2 and [(14)Mg(THF) 3 ] at 2.156(5)Å and 2.113(4)Å resp. are as expectedly significantly shorter than the ones measured in the dimers [(6a)Mg] 2 and [(10)Mg] 2 at 2.225(2)Å (av.) and 2.267(3)Å (av.). Electronic structureThe question of the nature of the bond between the AE metal and C was addressed. Harder et al.performed a DFT study first on models of [(6a)Ca] 2 and [(6f)Ca] where H atoms were considered in place of the real phenyl groups at P and groups (SiMe 3 and Ar resp.) at N. 49 In the case of the monomeric complex [(6f)Ca], the solvent molecules were not taken into account. Not surprising in light of the difference of electronegativity of the elements, the charge at C varied between -1.623 (monomer) and -1.847 (dimer) whereas charge at Ca varied between +1.760 (monomer) and +1.821 (dimer). The Ca-C bond was thus described as highly ionic. The calculations with the full dimeric system were carried out, and a slightly reduced charge was calculated at C (-1.778). The NPA charges were also compared to the ones in neutral 6aH 2 and the [Ca(6aH) 2 ] complex. Expectedly the charge at C goes from -1.079 to -1.409 to -1.778 (in 6aH2, [Ca(6aH) 2 ], [Ca(6a)] 2 resp.). The charge at N also increases (-1.474 to -1.580 to -1.665 resp.) upon deprotonation at C. Conversely, the charge at P varies but to a small extent (+1.747 to +1.727 to +1.7...

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confidence: 78%

Section: ) the Formation Of [256c]mentioning

confidence: 99%

Section: Reactivity Of Double Ylides Toward Main Group Elementsmentioning

confidence: 99%

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Geminal Dianions Stabilized by Main Group Elements

2019

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Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

et al. 2017

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The addition of acyclotriphosphine to abroad range of nitriles gives access to the first examples of free 1-aza-2,3,4triphospholenes in ar apid, ambient temperature,o ne-pot, high-yield protocol. The reaction produces electron-rich heterocycles (four lone pairs) and features homoatomic s-bond heterolysis,t herebyc ombining the key features of the 1,3dipolar cycloaddition chemistry of azides and cyclopropanes. Also reported is the first catalytic addition of PÀPbonds to the CNbond. The coordination chemistry of the new heterocycles is explored.

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Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

et al. 2017

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. [a] Vincent T. Annibale, [a] Natalie E. Pridmore, [a] Alex M. Oliver, [a] and Ian Manners* [a] Abstract: We report the addition of a cyclotriphosphine to a broad range of nitriles giving access to the first examples of free 1-aza-2,3,4-triphospholenes in a rapid, ambient temperature, one-pot, high-yield protocol. The reaction produces electron-rich heterocycles (four lone pairs) and features homoatomic -bond heterolysis, thereby combining the key features of the 1,3-dipolar cycloaddition chemistry of azides and cyclopropanes. We also report the first catalytic addition of P-P bonds to the CN triple bond. The coordination chemistry of the new heterocycles is explored.

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Selective and Reversible Fluoride Complexation from Water by a Cyclic Tri(phosphonio)methanide Dication

Abstract: Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 3 publications

References 68 publications

Geminal Dianions Stabilized by Main Group Elements

Geminal Dianions Stabilized by Main Group Elements

Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main‐Group Catalysis

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