Carbeniophosphanes and their carbon → phosphorus → metal ternary complexes

Canac, Yves; Maaliki, Carine; Abdellah, Ibrahim; Chauvin, Rémi

doi:10.1039/c1nj20808j

Cited by 86 publications

(51 citation statements)

References 91 publications

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“…The significant shift of the 31 P signal with respect to the free bis-ylide is in agreement with the expected ylide-rhodium complex structure. [13] Only the high-field value of the 103 Rh NMR chemical shift for 15 (δ = +477 ppm) with respect to the ortho-disubstituted species (δ = +983 ppm) [6] could be due to the cone shielding effect of the phenylene bridge, which is more sterically constrained above the Rh atom in 15 than in the ortho isomer. 5 Hz).…”

Section: Dimethylated M-phenylene-diphosphonium 13mentioning

confidence: 99%

Bis‐Ylide Ligands from Acyclic Proximal Diphosphonium Precursors

et al. 2012

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Keywords: Ylides / Ylide ligands / Phosphorus / Rhodium / Electrostatic interactions 1,2-or 1,3-Phenylene-diphosphonium bis-ylides have been prepared and their stabilities compared by analysis of the effects of the substitution pattern of the phenylene bridge and the steric hindrance of the P-alkyl substituents in the diphosphonium precursors RPh 2 P + (C 6 H 4 ) + PPh 2 RЈ (R,RЈ = Me, Et). In the o-phenylene series, the vicinity of the phosphorus centers allows the distal P + /Ccharge separation of the mono-ylide intermediate to be canceled by the formation of a cyclic ylidophosphorane. The ring strain in the latter was released through phenylene-P(σ 5 ) bond cleavage to afford relaxed diphosphonium bis-ylides, which were isolated as [a] 4058 Scheme 3. Preparation of the acyclic diphosphoniums 10 and 11 from o-dppb via the mono-ethyl phosphonium 9. .org phonium ylides. In contrast, in the m-phenylene series, in which the two phosphonium centers are in remote positions, the bis-ylide could be fully characterized. By reaction with a cationic rhodium(I) precursor, the latter bis-ylide was shown to act as a strongly donating carbon ligand, generalizing recent observations in the ortho series. [6] The role of steric and electrostatic interactions in the control of structural and reactivity features of acyclic proximal diphosphoniums has been highlighted herein. Experimental SectionGeneral: Diethyl ether, toluene, and thf were dried and distilled from sodium/benzophenone, pentane, dichloromethane, 1,1,2,2-tetrachloroethane (tce), and acetonitrile over P 2 O 5 . All other reagents were used as commercially available. All reactions were carried out under argon using Schlenk and vacuum-line techniques. 1 H, 13 C, and 31 P NMR spectra were recorded with Bruker DPX 300 and Avance 500 spectrometers. Chemical shifts (δ) are given in ppm with positive values to high frequency measured relative to tetramethylsilane for 1 H and 13 C NMR, and to H 3 PO 4 for 31 P NMR. Coupling constants (J) are given in Hz. 103 Rh chemical shifts are given to high frequency from δ( 103 Rh) = 3.16 MHz.Phosphonium 9: Ethyl trifluoromethanesulfonate (574 μL, 4.48 mmol) was added to a solution of 1 (2.0 g, 4.48 mmol) in tce (12.0 mL) and the solution was then stirred for 12 h at 110°C. After evaporation of the solvent, the solid residue was washed with Et 2 O (30.0 mL), affording 9 as a white powder (2.41 g, 86 %); m.p. 68-69°C. 1 H NMR (CD 3 CN, 25°C): δ = 7.85-7.50 (m, 14 H, H ar ), 7.42-7.22 (m, 6 H, H ar ), 6.99-6.90 (pseudo-t, J HH = J HP+ = 6.9 Hz, 4 H, H ar ), 3.57 (dq, J HH = 7.5, J HP+ = 12.9 Hz, 2 H, CH 2 ), 1.37 (dt, J HH = 7.5, J HP+ = 20.4 Hz, 3 H, CH 3 ) ppm. 13 C NMR (CD 3 CN, 25°C): δ = 142.8 (dd, J CP+ = 14.9, J CP = 14.9 Hz, C), 139.2 (d, J CP+ = 11.3 Hz, CH ar ), 136.5 (pseudo-t, J CP+ = J CP = 11.8 Hz, C), 135.1 (d, J CP+ = 2.8 Hz, CH ar ), 134.5 (d, J CP+ = 2.9 Hz, CH ar ), 133.3 (dd, J CP+ = 9.6, J CP = 1.9 Hz, CH ar ), 133.0 (d, J CP = 19.1 Hz, CH ar ), 131.6 (d, J CP = 9.9 Hz, CH ar ), 131.3 (d, J CP+ = 12.4 Hz, CH ar ), 13...

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Section: Dimethylated M-phenylene-diphosphonium 13mentioning

confidence: 99%

Bis‐Ylide Ligands from Acyclic Proximal Diphosphonium Precursors

et al. 2012

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“…This effect can be explained by the positive charge in the imidazoliumyl moiety . Thus, these types of compounds are used as electron‐poor ligands in organometallic chemistry and homogeneous catalysis, which was thoroughly reviewed by Renaud and Gailland and Chauvin and co‐workers …”

Section: Imidazoliumyl‐substituted Phosphorus Compoundsmentioning

confidence: 99%

“…In extension to the known catalysts, Alcarazo and co‐workers introduced a chiral TADDOL (α,α,α′,α′‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol) moiety to synthesize the corresponding imidazoliumyl‐substituted phosphonites 91 a – e [SbF 6 ] (Scheme ) . The diols 89 a – e are condensed with PCl 3 to give the respective chlorophosphanes 90 a – e , which are subsequently reacted with one equivalent of NHC 1 in the presence of NaSbF 6 to give 91 a – e [SbF 6 ].…”

Section: Imidazoliumyl‐substituted Phosphorus Compoundsmentioning

confidence: 99%

Recent Advances in Imidazoliumyl‐Substituted Phosphorus Compounds

Schwedtmann

Zanoni

Weigand

2018

Chemistry An Asian Journal

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This review aims to highlight the recent developments in the chemistry of selected imidazoliumyl-substituted phosphorus compounds. The synthetic approaches for their preparation with phosphorus in various oxidation states and coordination environments are discussed. Their intriguing properties and versatile chemistry strongly depends on the bonding motif at the P atoms, which is given special focus.

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“… The synthesis of imidazoliophosphines 8 and related 10 through alternative routes: A) from imidazol‐2‐type ylidenes 5 and related 9 , B) from 2‐carboxyl‐ or 2‐trimethylsilylimidazolium salts 6 , and C) from 2‐phosphinoimidazoles 7 …”

Section: Carbeniophosphinesmentioning

confidence: 99%

Carbeniophosphines versus Phosphoniocarbenes: The Role of the Positive Charge

Canac

2018

Chemistry An Asian Journal

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The chemistry of carbeniophosphines and phosphoniocarbenes, which have general structures derived formally from the three-component "carbene/phosphine/positive charge" association, is presented. These two complementary classes of carbon-phosphorus-based ligands, defined by the presence of an inverted cationic coordinating structure (C ∼P: vs. P ∼C:) have the common purpose of positioning a positive charge in the vicinity of the metal center. Through selected examples, the synthetic methods, coordination properties, and general reactivity of both cationic species is described. Particular emphasis is placed on the influence of the positive charge on the respective chemical behavior of the two classes of compound.

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Carbeniophosphanes and their carbon → phosphorus → metal ternary complexes

Cited by 86 publications

References 91 publications

Bis‐Ylide Ligands from Acyclic Proximal Diphosphonium Precursors

Bis‐Ylide Ligands from Acyclic Proximal Diphosphonium Precursors

Recent Advances in Imidazoliumyl‐Substituted Phosphorus Compounds

Carbeniophosphines versus Phosphoniocarbenes: The Role of the Positive Charge

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