137846-38-9

Usage

Uses

Used in Pharmaceutical Industry:
Pd(OTf)2(dippp) is used as a catalyst for the synthesis of phenanthridines, which are important compounds in the pharmaceutical industry. The application reason is that it facilitates the reaction between 2-halogeno-N-Ms arylamines and benzyl halides/sulfonates via nucleophilic substitution, followed by C-H functionalization and aromatization reaction. This process allows for the efficient and selective synthesis of phenanthridines, which have potential applications in the development of new drugs and therapeutic agents.
Used in Chemical Synthesis:
In the field of chemical synthesis, Pd(OTf)2(dippp) is used as a catalyst to promote various organic reactions, such as cross-coupling reactions, C-H activation, and carbonylation reactions. The application reason is its ability to provide high selectivity and reactivity, leading to the formation of desired products with minimal side reactions. This makes it a valuable tool for the synthesis of complex organic molecules and advanced materials.
Used in Research and Development:
Pd(OTf)2(dippp) is also used in research and development settings, where it serves as a versatile catalyst for exploring new reaction pathways and developing innovative synthetic methods. The application reason is its unique catalytic properties, which enable chemists to study the underlying mechanisms of various reactions and design new strategies for the synthesis of complex molecules and materials.

Upstream product

• 59831-02-6 bis(diphenylphosphino)propanepalladium(II) dichloride 
• 2923-28-6 silver trifluoromethanesulfonate 
• 333-27-7 methyl trifluoromethanesulfonate 
• 6737-42-4 1,3-bis-(diphenylphosphino)propane 
• 59831-02-6 dichloro [1,1'-bis(diphenylphosphino)propane]palladium(II) 

Downstream Products

• 161405-44-3 Pd(((C₆H₅)2PCH₂)2CH₂)(H₂O)(OSO₂CF₃)⁽¹⁺⁾*CF₃SO₃^(1-)=[Pd(((C₆H₅)2PCH₂)2CH₂)(H₂O)(OSO₂CF₃)]OSO₂CF₃ 

Relevant academic research and scientific papers

Unusual anion effects on the solution-behavior of cyclodimeric Pd(II) complex

Unusual anion effects on the solution-behavior of [(dppp)Pd(m-ptms)]2(X)4 (dppp = 1,3-bis(diphenylphosphino)propane; m-ptms = 1,3-bis(3-pyridyl)tetramethyldisiloxane; X- = CF3 SO3-, PF

Anion transport across phospholipid membranes mediated by a diphosphine-Pd(ii) complex

The [Pd(dppp)(OTf)2] complex acts as an efficient transporter of halide anions, in particular the biologically relevant chloride anion, across a phospholipid bilayer. This journal is the Partner Organisations 2014.

Triphenylene based metal-pyridine cages

C3-symmetric pyridine containing tris-benzyl-O-substituted hexahydroxytriphenylene derivatives were prepared and used in combination with square-planar Pd(II) and Pt(II) complexes for the self-assembly of molecular cages in solution. The formation of a trigonal bipyramid M3L2 cage was demonstrated by multinuclear NMR analyses and pseudo 2D DOSY experiments and supported by semi-empirical calculations.

Self-Assembled Novel BODIPY-Based Palladium Supramolecules and Their Cellular Localization

Four new palladium metal supramolecules with triangular/square architectures derived from boron dipyrromethane (BODIPY) ligands were synthesized by self-assembly and fully characterized by 1H and 31P NMR, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. These supramolecules were more cytotoxic to brain cancer (glioblastoma) cells than to normal lung fibroblasts. Their cytotoxicity to the glioblastoma cells was higher than that of a benchmark metal-based chemotherapy drug, cisplatin. The characteristic green fluorescence of the BODIPY ligands in these supramolecules permitted their intracellular visualization using confocal microscopy, and the compounds were localized in the cytoplasm and on the plasma membrane.

Cis-specific hydrofluorination of alkenylarenes under palladium catalysis through an ionic pathway

This paper describes the hydrofluorination of alkenes through sequential H- and F+ addition under palladium catalysis. The reaction is cis specific, thus providing access to benzylic fluorides. The mechanism of this reaction involves an ionic pathway and is distinct from known hydrofluorinations involving radical intermediates. The first catalytic enantioselective hydrofluorination is also disclosed. See attached PdF: A series of benzylic fluorides was prepared by hydrofluorination which proceeds through a PdII/IV catalytic manifold. The method is mechanistically distinct from previously reported radical hydrofluorination, and is characterized by its clean regioselectivity and unique cis stereospecificity. The first example of enantioselective net HF addition onto 2-vinylnaphthalene is also disclosed.

Palladium catalysed alkyne hydrogenation and oligomerisation: A parahydrogen based NMR investigation

The role phosphine ligands play in the palladium(ii)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL′)(OTf)2 (1a-e) [LL′ = dcpe (PCy2CH 2CH2PCy2), dppe, dppm, dppp, cppe (PCy 2CH2CH2PPh2)] are used. Alkyl palladium intermediates of the type [Pd(LL′)(CHPhCH2Ph)](OTf) (2 and 3) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the α-H of the alkyl ligand of 2a (LL′ = dcpe) and linkage isomer 2e′ (LL′ = cppe) into trans-stilbene on the NMR timescale. Activation parameters (ΔH≠ and ΔS≠) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD 2Cl2. All five of the phosphine systems described are less active than those based on bcope [where bcope is (C8H 14)PCH2-CH2P(C8H14)] and tbucope [where tbucope is (C8H 14)PC6H4CH2P(tBu) 2]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL′)(PhCH-CHPh-CPh=CHPh)+ (4) also being shown to play a role in the alkyne dimerisation step.

Self-assembly and anion encapsulation properties of cavitand-based coordination cages

Two novel classes of cavitand-based coordination cages 7a-j and 8a-d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P-M-P angle close to 90° between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic 1H and 19F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d revealed the presence of a single triflate anion encapsulated. Guest competition experiments revealed that the encapsulation preference of cages 7b,d follows the order BF4- > CF3SO3- ? PF6- at 300 K. ES-MS experiments coupled to molecular modeling provided a rationale for the observed encapsulation selectivities. The basic selectivity pattern, which follows the solvation enthalpy of the guests, is altered by size and shape of the cavity, allowing the entrance of an ancillary solvent molecule only in the case of BF4-.

Self-assembly of cationic, tetranuclear, Pt(II) and Pd(II) macrocyclic squares. X-ray crystal structure of [Pt2+(dppp)(4,4′-bipyridyl)2-OSO 2CF3]4

The preparation, characterization, and some chemistry of a series of unique cationic, tetranuclear, Pt(II)-and Pd(II)-based macrocyclic squares are reported. A variety of bidentate ligands (bipyridine, diazapyrene, dicyanobenzene, and dicyanobiphenyl) are interacted with the square-planar cis-bis(phosphine) Pt and Pd bis(triflate) complexes in organic solvents at room temperature, resulting in molecular squares in high isolated yields via self-assembly. All molecular squares are robust air- and water-stable microcrystalline solids with decomposition points mostly above 200 °C. They are generally soluble in polar organic solvents but not in water or nonpolar solvents like pentane, toluene, and ether. The cyano-based macrocycles are highly fluxional in solution, whereas the bipy and related systems are more stable. Concentration-dependent chemical shifts are observed for the ortho and meta protons of 1,5-dihydroxynaphthalene, indicating host-guest interactions and inclusion phenomena. X-ray crystal structures are reported for the molecular square [(dppp)Pt(bipy)]48+8-OSO2CF 3 (15a), as well as a dinuclear dicyanobenzene complex 25 and the [(dppp)M(pyrazine)]2+2-OSO2CF3 (M = Pt, Pd) complexes 20a,b.

Influence of ligands and anions on the insertion of alkenes into palladium-acyl and palladium-carbomethoxy bonds in the neutral complex (dppp)Pd(C(O)CH3)Cl and the ionic complexes +SO3CF3- (P-P = dppe, dppp, dppb; R = C(O)CH3, L= CH3CN, PPh3; R = C(O)OCH3, L = PPh3)

Insertions of alkenes in Pd-acetyl bonds of (dppp)Pd(C(O)CH3)Cl and +SO3CF3- (P-P = dppe, dppp, dppb; L = CH3CN, PPh3) have been studied as a function of the ligand, the anion and the alkene.The neutral acetyl complex (dppp)Pd(C(O)CH3)Cl underwent insertion only with norbornadiene and norbornene, while the ionic acetyl complexes +SO3CF3- (P-P = dppe, dppp, dppb) reacted with norbornadiene, norbornene, styrene, cis-stilbene, 1-pentene, 3,3-dimethyl-1-butene, vinyltrimethylsilane, methyl vinyl ketone, methyl acrylate, diethyl fumarate, and diethyl maleate.This insertion was observed to give an intermediate in which there was intramolecular coordination of the ketone oxygen atom to the palladium centre.In monosubstituted alkenes the acetyl group migrates to the unsubstituted carbon atom.The insertion products underwent β-elimination to give (trans) unsaturated ketones and a palladium hydride.The rate of this elimination was higher for complexes containing ligands L-L with smaller bite angles (dppe > dppp), and the rate of insertion showed the reverse order.The carbomethoxy complexes +SO3CF3- (P-P = dppe, dppp, dppb) were prepared from (P-P)Pd(SO3CF3)2 with CO, CH3OH and PPh3.The carbomethoxy complex reacted with norbornadiene to give a carbomethoxy oxygen-coordinated intermediate.The carbomethoxy complexes were less reactive than the analogous acetyl complexes towards alkenes.