C–F Bond Activation by Transient Phosphenium Dications

Đorđević, Nemanja; Tay, Madelyn Qin Yi; Muthaiah, Senthilkumar; Ganguly, Rakesh; Dimić, Dušan; Vidović, Dragoslav

doi:10.1021/ic5031125

Cited by 20 publications

(4 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Vidović reported the synthesis and characterization of the chlorinated cations [( 130 )P III (Cl)Ph] + ( 554a ) and [( 130 )P III (Cl)(4–F-C 6 H 4 )] + ( 555b ) from 130 and the appropriate Cl 2 PAr in excess (Scheme ). In addition to the indicative NMR pattern, the atom connectivity of [ 555b ][Cl] was established by XRD analysis. Heating of [ 554a ][Cl] at 100 °C overnight in presence of [Na][BAr F 4 ] (3 equiv) produced the fluorinated cation 557a in minimal amounts that precluded its isolation.…”

Section: Geminal Dianions Of Type III (A and B: Cationic Fragments)mentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

View full text Add to dashboard Cite

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...

show abstract

Section: Geminal Dianions Of Type III (A and B: Cationic Fragments)mentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

View full text Add to dashboard Cite

show abstract

“…In a related sense, Gudat has pioneered the reactivity of the masked phosphenium cations derived from N‐heterocyclic phosphines . Recently the Vidović group showed that P III dications exhibit stoichiometric activation of C−F bonds at 100 °C, albeit with a limited scope of substrates (only α‐phenyl C−F bonds) . The same group also showed abstraction of hydrides from silanes and amine/pyridyl‐boranes under ambient conditions .…”

Section: Figurementioning

confidence: 99%

Catalytic Hydrodefluorination of C−F Bonds by an Air‐Stable P^III Lewis Acid

Chitnis

Krischer

Stephan

2018

Chemistry A European J

View full text Add to dashboard Cite

Catalytic hydrodefluorination (HDF) of unactivated fluoroalkanes or CF -substituted aryl species is performed using the P Lewis acids, [(bipy)PPh] (1 ) and [(terpy)PPh] (2 ) under mild conditions (25 or 50 °C). Mechanistic studies indicate that activation of C-F bond by the P center is key. Particularly noteworthy is that the catalyst 2[B(C F ) ] is air-stable and readily accessible from bench-stable, commercially available reagents in one-step and can be used without isolation.

show abstract

“…Although previously unknown, Vidovic and co‐workers reported the first example of C−F bond activation by a Lewis acidic P III species in 2015. These authors described the formation of the transient phosphenium dications, [PhP(C(PPh 3 ) 2 )] 2+ , generated by chloride abstraction from the corresponding monocation [PhPCl(C(PPh 3 ) 2 )] 4 . The dication was intercepted with the addition of PMe 3 as [PhP(PMe 3 )(C(PPh 3 ) 2 )] 2+ 5 (Scheme ), but the chemistry showed an interesting anion dependence.…”

Section: Phosphorus(iii) Cationic Lewis Acidsmentioning

confidence: 99%

C−F Bond Activation Mediated by Phosphorus Compounds

Bayne

Stephan

2019

Chemistry A European J

View full text Add to dashboard Cite

The activation and functionalization of CÀFb onds has garnered significant attention in the scientificc ommunity as as trategy to mitigate toxicitya nd environmental concerns, as well as provide new pathways to agro-and pharmaceuticalc hemicals and materials. Although severalt ransition-metal-based systemsh ave been developed for this transformation,t he use of main-group compoundsr emains less explored. In recent years, several strategies for CÀF bond activation have focused on the use of phosphorusbased reagents. In this Minireview,a no verview of strategies is provided that exploits P V andP III -based Lewis acids as well as P III Lewis bases in frustrated Lewis pair (FLP) protocols for hydrodefluorination, CÀCc ouplings andC ÀFd erivatizations.

show abstract

C–F Bond Activation by Transient Phosphenium Dications

Cited by 20 publications

References 43 publications

Geminal Dianions Stabilized by Main Group Elements

Geminal Dianions Stabilized by Main Group Elements

Catalytic Hydrodefluorination of C−F Bonds by an Air‐Stable P^III Lewis Acid

C−F Bond Activation Mediated by Phosphorus Compounds

Contact Info

Product

Resources

About

C–F Bond Activation by Transient Phosphenium Dications

Cited by 20 publications

References 43 publications

Geminal Dianions Stabilized by Main Group Elements

Geminal Dianions Stabilized by Main Group Elements

Catalytic Hydrodefluorination of C−F Bonds by an Air‐Stable PIII Lewis Acid

C−F Bond Activation Mediated by Phosphorus Compounds

Contact Info

Product

Resources

About

Catalytic Hydrodefluorination of C−F Bonds by an Air‐Stable P^III Lewis Acid