Synthesis, Structure, and Reactivity of a Stable Phosphonium–Sulfinyl Yldiide

Garduno-Alva, Azucena; Lenk, Romaric; Escudié, Yannick; González, Martha Letícia Gaeta; Bousquet, Laura; Saffon‐Merceron, Nathalie; Toledano, Cecilio Álvarez; Bagan, Xavier; Branchadell, Vicenç; Maerten, Eddy; Baceiredo, Antoine

doi:10.1002/ejic.201700648

Cited by 15 publications

(15 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A sulfinyl-stabilized yldiide was reported by Maerten, Baceiredo and coworkers. 39 Lithium yldiide 16 was synthesized by deprotonation with n -BuLi and showed a dimeric structure with a Li 2 O 2 core and decreased P–C and C–S bond lengths owing to the increased negative character at the ylidic carbon center.…”

Section: Alkali Metal Yldiidesmentioning

confidence: 99%

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds

2021

View full text Add to dashboard Cite

show abstract

Section: Alkali Metal Yldiidesmentioning

confidence: 99%

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds

2021

View full text Add to dashboard Cite

show abstract

“…Apart from Bertrand's α-lithiomethylenephosphorane 79, obtained by formal 1,2-addition of n-butyllithium to an in-situ generated trimethylsilyl-phosphanylcarbene (scheme 93), 196 all of them are obtained following the previous strategy, i.e. deprotonation of an ylide by nbutyllithium 195 or variously metallated amides. 194 In the latter cases, X-ray diffraction studies showed the coordination of the alkali metal by both the carbon and one oxygen from the sulfoxide (in 80) or sulfone (in 81) stabilizing moiety.…”

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

“…The C−Au bond lengths [2.056(4) and 2.071(4) Å] are shorter than those observed in the related carbodisphosphorane‐ and carbodicarbene‐diaurated complexes (2.074, 2.078 Å and 2.080, 2.103 Å respectively). The aurophilic interaction is classical with Au1‐Au2 distance of 3.018(1) Å, which is in the range of other gem ‐diaurated carbones (2.952–3.143 Å) . Finally, the P1−C1 [1.781(4) Å] and the S1−C1 [1.737(4) Å] bonds lengths are significantly longer than in 1 , typical for single bonds (P−C: 1.79–1.82 Å and S−C: 1.73–1.75 Å) confirming that the two lone pairs are involved in the formation of complex 4 .…”

Section: Figurementioning

confidence: 97%

“…The phosphine/sulfoxide carbon(0) complex 2 was prepared in two steps from the corresponding chlorophosphonium and methyldiphenylsulfoxonium salts in presence of 2 equivalents of a non‐nucleophilic strong base (LDA) (Scheme ) . In a second step, the deprotonation of salt 1 was performed in THF solution at RT, either with potassium hydride (KH) or potassium hexamethyldisilazane (KHMDS) leading to the selective formation of 2 , which was isolated in 69 % overall yield.…”

Section: Figurementioning

confidence: 99%

Phosphine/Sulfoxide‐Supported Carbon(0) Complex

González

Bousquet

Hameury

et al. 2018

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

A new carbon(0) complex 2 with two different L ligands, a phosphine and a sulfoxide, was synthesized and fully characterized. This new type of carbone exhibits excellent coordination ability, in contrast to the related phosphine/sulfide-supported carbon(0) complexes. Several organometallic complexes were isolated and, of special interest, the ν (CO) value of Rh -dicarbonyl complex indicates that 2 has a donor capability superior to classical NHCs.

show abstract

Synthesis, Structure, and Reactivity of a Stable Phosphonium–Sulfinyl Yldiide

Cited by 15 publications

References 64 publications

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds

Phosphorus-ylides: powerful substituents for the stabilization of reactive main group compounds

Geminal Dianions Stabilized by Main Group Elements

Phosphine/Sulfoxide‐Supported Carbon(0) Complex

Contact Info

Product

Resources

About