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Шмидт, Ф. К.; Belykh, L. B.; Goremyka, T. V.

doi:10.1023/a:1014223932310

Cited by 6 publications

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“…Surprisingly, little is known about complexes of Pd(II) with PPh 2 PPh 2 or its oxide; [47][48][49][50] none of them contain a palladacycle. The structure of compound 19 as a mononuclear cyclopalladated complex with PPh 2 P(O)Ph 2 as an auxiliary ligand is proposed on the basis of the 1 H, 13 C{ 1 H}, 31 P{ 1 H}, and 2D NMR spectra.…”

Section: Resultsmentioning

confidence: 99%

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

2009

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Reactions of the cyclopalladated dimer {Pd(η2-L1)(μ-Cl)}2 (7) derived from N,N-dimethylbenzylamine (HL1) with lithium diphenylphosphide were studied under varied conditions. The LiPPh2 reagents used were purchased from Sigma-Aldrich Co. or synthesized from PPh3, ClPPh2, or HPPh2 by known general methods. Depending on the source of lithium phosphide, solvent, and reagent ratio, reactions of LiPPh2 with complex 7 resulted in the formation of different products. The commercial LiPPh2 solutions reacted with compound 7 and several other cyclopalladated dimeric complexes in THF to form the corresponding mononuclear derivatives with Ph2P(CH2)4OH as an auxiliary ligand, Pd(η2-L)Cl{PPh2(CH2)4OH}. The monophosphido-bridged analogue of dimer 7, {Pd(η2-L1)}2(μ-Cl)(μ-PPh2) (17), was the most common product of the 1:2 reactions of dimer 7 with other LiPPh2 solutions in THF. ortho-(Diphenylphosphino)-N,N-dimethylbenzylamine (20) was obtained in the reactions of complex 7 with the synthesized solutions of LiPPh2 using a 1:4.5 molar ratio of the reagents in THF or a 1:2 ratio in toluene. Possible mechanisms of these reactions are discussed.

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Section: Resultsmentioning

confidence: 99%

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

2009

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Redox Chemistry and Electrochemistry of Metal Enolates

Pampaloni

Zanello

2010

Patai's Chemistry of Functional Groups

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Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R₂PH (R = C₂F₅, C₆F₅, (CF₃)₂C₆H₃)

et al. 2019

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Electron-withdrawing substituents R in complexes [L n M(PR 2 )] influence the P-M bond length due to a decreased σ-donation and enhanced π-back-bonding, leading to an increased Lewis acidity of the metal ion and therefore strengthening the M-L bond to electron-rich ligands L. This influences the Lewis acidity and the redox behavior of corresponding transition-metal complexes, which is important for the design of optimized catalytic systems. To investigate this effect, the electronpoor phosphanes R 2 PH with R = C 2 F 5 , C 6 F 5 , 2,4-(CF 3 ) 2 C 6 H 3 were treated with Pd(F 6 acac) 2 (F 6 acac = hexafluoroacetylacetonato) [a] 3904 and Pd(acac) 2 (acac = acetylacetonato). While the reaction of the phosphanes with Pd(F 6 acac) 2 in all cases yielded the corresponding phosphido-bridged dinuclear palladium complexes [{(F 6 acac)Pd[μ-(PR 2 )]} 2 ], the compounds obtained in the reaction with Pd(acac) 2 were structurally more diverse. For R = C 2 F 5 , the dinuclear palladium complex [{(acac)Pd{μ-[P(C 2 F 5 ) 2 ]}} 2 ] was obtained, while the reaction with (C 6 F 5 ) 2 PH yielded a trinuclear palladium complex bridged by four phosphido units. All complexes were fully characterized, including X-ray crystallography.complexes with bridging dialkylphosphido units have been reported in the literature, [10] no X-ray structural data are available.The most conducive and feasible procedure to synthesize dinuclear palladium(II) complexes with bridging phosphido units was devised by Shmidt, Belykh and Goremyka. [11] They precisely describe the reaction of Ph 2 PH with Pd(acac) 2 (acac = acetylacetonato) which led to di-and trinuclear palladium complexes bridged by diphenylphosphido units. A related complex featuring chelating F 6 acac ligands (F 6 acac = hexafluoroacetylacetonato), albeit synthesized differently, was published by Röschenthaler et al. including an X-ray structural investigation. [12] Perfluoroalkyl and -aryl groups distinctly influence the electronic properties of phosphane ligands. The HOMO, which correlates with the negative ionization energy, as well as the LUMO, which correlates with the negative electron affinity, of the fluorinated phosphane derivatives are lowered (Figure 1, left), which is expressed in a decreased nucleophilicity of the Eur. 3905Scheme 3. Synthesis of palladium complex 4.Scheme 4. Synthesis of the trinuclear palladium complex 5.Scheme 5. Synthesis of tetrakis[2,4-bis(trifluoromethyl)phenyl]diphosphane, 6.

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Cited by 6 publications

References 8 publications

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

Redox Chemistry and Electrochemistry of Metal Enolates

Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R₂PH (R = C₂F₅, C₆F₅, (CF₃)₂C₆H₃)

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Cited by 6 publications

References 8 publications

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

Reactions of Cyclopalladated Complexes with Lithium Diphenylphosphide

Redox Chemistry and Electrochemistry of Metal Enolates

Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R2PH (R = C2F5, C6F5, (CF3)2C6H3)

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Phosphido‐Bridged Di‐ and Trinuclear Palladium Complexes from Electron‐Poor Phosphanes R₂PH (R = C₂F₅, C₆F₅, (CF₃)₂C₆H₃)