Phosphine/Sulfoxide‐Supported Carbon(0) Complex

González, Martha Letícia Gaeta; Bousquet, Laura; Hameury, Sophie; Toledano, Cecilio Álvarez; Saffon‐Merceron, Nathalie; Branchadell, Vicenç; Maerten, Eddy; Baceiredo, Antoine

doi:10.1002/chem.201705557

Cited by 11 publications

(10 citation statements)

References 89 publications

(26 reference statements)

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“…407 The presence of intramolecular base in ] supported by the P,S IV -mixed bis(ylide) 258 and the phosphallene 264b were prepared. [323,324] In 2011, Gandon used CDP 130 as ancillary ligand in gold catalysis. 409 In this thorough study, the au- The first report dealing with carbodiphosphorane containing silver complexes appeared in 1983.…”

Section: Coordination To Group 11 (Coinage) Metalsmentioning

confidence: 99%

“…In 2018, Maerten and Baceiredo have accomplished the twostep synthesis of the mixed P,S IV -bis(ylide) 258 starting from chlorophosphonium salt [240b] [Cl] and the methyldiphenylsulfoxonium salt [257][OTf] (Scheme 163). 323 The ylide [258-H][OTf] was prepared by addition of LDA (2 equiv) to a mixture of salts [240b] [Cl] and [257][OTf] and subsequently transformed to bis(ylide) 258 upon deprotonation. After isolation (76%), 258 was fully characterized by HRMS analysis and multinuclear NMR experiments.…”

Section: Synthesis Of Geminal Dianions Of Type IIImentioning

confidence: 99%

“…312 [Cl] and the methyldiphenylsulfoxonium salt [257][OTf]. 323 The ylide [258-H][OTf] was prepared by addition of LDA (2 equiv.) to a mixture of salts…”

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confidence: 99%

“…This method was applied to acquire some insight on the electron donor ability of the P,C-bis(ylide) 264b, [324] and the P,Sbis(ylide)s 228b [308] and 258. [323] The complexes were synthesized according to two alternative routes. 393 Kaska studied the coordination chemistry of 130 towards cationic Pt(IV) complexes.…”

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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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Section: Coordination To Group 11 (Coinage) Metalsmentioning

confidence: 99%

Section: Synthesis Of Geminal Dianions Of Type IIImentioning

confidence: 99%

“…312 [Cl] and the methyldiphenylsulfoxonium salt [257][OTf]. 323 The ylide [258-H][OTf] was prepared by addition of LDA (2 equiv.) to a mixture of salts…”

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confidence: 99%

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confidence: 99%

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Geminal Dianions Stabilized by Main Group Elements

2019

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“…Baceirdo's research is centered on the chemistry of highly reactive species with specific electronic properties such as carbenes, ylides, and silylenes. He has reported in Chemistry—A European Journal on a phosphine/sulfoxide‐supported carbon(0) complex, and is co‐author of a report in Angewandte Chemie on reversible addition of CO 2 to a Si=O bond …”

Section: Awarded …mentioning

confidence: 99%