Extending the chemistry of carbones: P–N bond cleavage via an S<sub>N</sub>2′-like mechanism

Gurnani, Chitra; Đorđević, Nemanja; Muthaiah, Senthilkumar; Dimić, Dušan; Ganguly, Rakesh; Petković, Milena; Vidović, Dragoslav

doi:10.1039/c5cc03194j

Cited by 18 publications

(8 citation statements)

References 48 publications

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“…430,431 The same group reported the selective P−N bond activation instead of the P−Cl of MeNPCl 2 mediated by 130, yielding the cation [(130)P III Cl 2 ] + (563). 432 Theoretical investigations were carried out at the B3LYP/6-31G(d) level and pointed to the formation of 563 involving a seemingly S N 2′ mechanism via intermediate XXXII (see Scheme 228).…”

Section: Reactivity Of Double Ylides Toward Main Group Elementsmentioning

confidence: 99%

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: Reactivity Of Double Ylides Toward Main Group Elementsmentioning

confidence: 99%

Geminal Dianions Stabilized by Main Group Elements

2019

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“…The starting material for the reaction, [{(Ph 3 P) 2 C}PCl 2 ][Cl], was synthesized according to the earlier mentioned procedure. [141] Similarly, anion exchange was achieved with NaBAr X 4 (X= F, Cl).…”

Section: Synthetic Methodsmentioning

confidence: 99%

“…The peak was within the reported range for the two-coordinate phosphenium cations, and more than 200 ppm downfield shifted, as compared to the analogous signal for the 2c + . [141] In addition, δ P values for the central P were found to be . Results of 31 P NMR spectroscopy indicated complete conversion of the starting material and excellent correlation with the previously reported [142] NMR data (δ P for P central ~ 356 ppm).…”

Section: Synthetic Viabilitycounterionsmentioning

confidence: 97%

“…) involved the addition of 2.1eq of either AlCl 3 or NaBAr F 4 to the DCM solution containing the corresponding monocationic precursor [2c][Cl] . [141] The appearance of the 31 P NMR signal for the central P atom at around δ P 356 ppm was the most indicative piece of evidence for the formation of the two-coordinate phosphorus species. The peak was within the reported range for the two-coordinate phosphenium cations, and more than 200 ppm downfield shifted, as compared to the analogous signal for the 2c + .…”

Section: Synthetic Viabilitycounterionsmentioning

confidence: 99%

“…Young NMR tube using about 1 mL of DCM followed by the addition of 2.1 equiv of an anion source. The reaction mixture was left to react for about 6 h by continuous rotation of the NMR tube, and the reaction progress was followed by 31 ] was prepared according to the previously reported procedure [141] and used in situ for the preparation of [31] were obtained.…”

Section: Preparation Of the Monocationic Precursors [2]clmentioning

confidence: 99%

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Molecules containing lewis acidic phosphorus - sites

Ilic¹

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Thank you to my Balkan and Russian friends, this journey would not be the same without all the coffee/tea breaks filled with laughter. Ivan Šolić, thank you for being my tech-saviour at the end. Completing this dissertation would be much more inconvenient without your generosity. I am aslo grateful for my Singaporean and international friends who I met here, whose help and company were of great value.

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Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

et al. 2021

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We report a combined experimental and theoretical study on the first examples of carbodicarbene (CDC)‐stabilized bismuth complexes, which feature low‐coordinate cationic bismuth centers with C=Bi multiple‐bond character. Monocations [(CDC)Bi(Ph)Cl][SbF6] (8) and [(CDC)BiBr2(THF)2][SbF6] (11), dications [(CDC)Bi(Ph)][SbF6]2 (9) and [(CDC)BiBr(THF)3][NTf2]2 (12), and trication [(CDC)2Bi][NTf2]3 (13) have been synthesized via sequential halide abstractions from (CDC)Bi(Ph)Cl2 (7) and (CDC)BiBr3 (10). Notably, the dications and trication exhibit C⇉ Bi double dative bonds and thus represent unprecedented bismaalkene cations. The synthesis of these species highlights a unique non‐reductive route to C−Bi π‐bonding character. The CDC‐[Bi] complexes (7–13) were compared with related NHC‐[Bi] complexes (1, 3–6) and show substantially different structural properties. Indeed, the CDC ligand has a remarkable influence on the overall stability of the resulting low‐coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.

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Extending the chemistry of carbones: P–N bond cleavage via an S_N2′-like mechanism

Cited by 18 publications

References 48 publications

Geminal Dianions Stabilized by Main Group Elements

Geminal Dianions Stabilized by Main Group Elements

Molecules containing lewis acidic phosphorus - sites

Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

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Extending the chemistry of carbones: P–N bond cleavage via an SN2′-like mechanism

Cited by 18 publications

References 48 publications

Geminal Dianions Stabilized by Main Group Elements

Geminal Dianions Stabilized by Main Group Elements

Molecules containing lewis acidic phosphorus - sites

Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry

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Extending the chemistry of carbones: P–N bond cleavage via an S_N2′-like mechanism