Ferrocenium hexafluorophosphate - ≥96% , CAS No.11077-24-0

CAS: 11077-24-0 Cat. No.: F338461 Fórmula: C₁₀H₁₀F₆FeP Peso molecular: 331 Número EC: 629-209-0 PubChem CID: 16212479

GRADE & PURITY ≥96%

Storage

Store at 2-8°C,Argon charged

Shipped In

Wet ice

Descripción general

Ferrocenyl hexafluorophosphate is a ferrocenium cation that has been used in the preparation of catalysts for the asymmetric epoxidation of olefins, carbonylation of nitroaromatic compounds, and isomerization of strained dienes.

Specifications

Especificaciones y pureza

≥96%

Condiciones de almacenamiento de almacenamiento

Store at 2-8°C,Argon charged

Enviado en

Wet ice

Este producto requiere envío en cadena de frío. Los servicios terrestres y otros servicios económicos no están disponibles.

Pureza

≥96%

Nombres e identificadores

Pubchem Sid

504768178

Pubchem Sid Url

https://pubchem.ncbi.nlm.nih.gov/substance/504768178

Sonrisas canónicas

C1=C[CH]C=C1.C1=C[CH]C=C1.F[P-](F)(F)(F)(F)F.[Fe]

InChIKey

PCJFEGIXYOQEQD-UHFFFAOYSA-N

INCHI

1S/2C5H5.F6P.Fe/c2*1-2-4-5-3-1;1-7(2,3,4,5)6;/h2*1-5H;;/q;;-1;

Isómeros SMILES

C1=C[CH]C=C1.C1=C[CH]C=C1.F[P-](F)(F)(F)(F)F.[Fe]

PubChem CID

16212479

Número ONU

3261

Grupo de embalaje

II

Peso molecular

331

Propiedades químicas y físicas

• Sensibilidad: air sensitive

Application Protocols

No validated bioassay protocols (e.g., WB, IHC, IF, FC) are applicable to this reagent.

General laboratory protocol sketch (literature) for a SET oxidation in MeCN:

• Dry a 50 mL Schlenk flask and charge with substrate (1.0 mmol) and anhydrous MeCN (10 mL).
• Cool to 0–5 °C under argon. Prepare a solution of ferrocenium PF6 (1.05–1.20 mmol) in dry MeCN (5 mL).
• Add oxidant solution dropwise over 20–30 min with stirring; maintain temperature.
• Stir 10–60 min, monitoring by TLC/UV–Vis. Warm to rt if needed to drive completion.
• Quench excess oxidant with a small amount of ferrocene, then concentrate under reduced pressure.
• Extract with hexanes/EtOAc to remove ferrocene (orange fraction) and isolate product by chromatography.

Note: This is general guidance only. Adapt stoichiometry, temperature, and solvent to the specific substrate and consult primary literature.

Biological Roles

This product is intended for research use only; no medical or clinical claims are made.

General/literature context:

• Ferrocene/ferrocenium couples are benchmarks in bioinorganic and bioelectrochemistry due to their reversible redox behavior and relatively well-behaved electron-transfer kinetics in organic media.
• Ferrocenium salts can oxidize electron-rich biomolecule models (e.g., thioethers, indoles) under nonaqueous conditions, serving as surrogates to study oxidative stress or radical-cation pathways in vitro.
• In electrochemical biosensors, ferrocene derivatives are widely used as redox mediators; ferrocenium formation is central to signal transduction. While ferrocenium PF6 itself is less common directly in aqueous biosensor operation (owing to water reactivity/solubility constraints), it is frequently used to benchmark mediator potentials and to prepare ferrocenyl-functionalized probes.
• The PF6− counterion is not biologically relevant and offers no buffering or coordination benefits; it is chosen for weak coordination and solubility in organic media.

Note: Any use involving biological matrices should consider incompatibility with water and potential PF6− hydrolysis; alternative counterions or solvent systems may be preferable for aqueous applications.

Buffer Applications

Ferrocenium hexafluorophosphate is not a buffering agent and is not typically used to prepare pH buffer systems. Its solubility and stability profile are poorly compatible with aqueous buffers, and PF6− offers no buffering capacity.

Practical guidance:

• For experiments requiring controlled pH, prepare the buffer separately (e.g., phosphate, acetate, HEPES) and, if redox steps are needed, consider organic-phase or biphasic electrochemical setups where ferrocenium-mediated steps are performed in a dry, aprotic phase.
• If redox mediators are needed in aqueous buffers, consider water-soluble ferrocene derivatives (e.g., ferrocene carboxylates, sulfonates) instead.

Green Alternatives

Sustainability considerations for ferrocenium PF6 as an oxidant center on solvent choice, counterion persistence, and metal content.

• Positives (general):
  • Iron-based; Fe is abundant and relatively low-toxicity compared to Ag(I), Sb(V), or Ru oxidants.
  • Outer-sphere mechanism often obviates need for halides or strong acids.
• Concerns:
  • PF6− is persistent; hydrolysis can generate HF under extreme conditions. Disposal should follow regulations for fluorinated salts.
  • Typical solvents (MeCN, DCM) pose health and environmental burdens.

Representative comparisons (literature; choose per chemistry):

• AgPF6 or NOPF6: stronger, but introduce Ag waste or nitrosating species—higher EHS burden than ferrocenium.
• Magic Blue (tris(4-bromophenyl)aminium hexachloroantimonate): powerful but uses Sb and brominated aromatics—less favorable EHS profile.
• DDQ: halogenated quinone; strong oxidant but generates chlorinated waste.
• Oxygen or air (with catalyst): green terminal oxidants for some substrates; may not mimic clean outer-sphere SET and can change selectivity.
• TEMPO/oxammonium salts: metal-free options for alcohol oxidations, but mechanistically different.

Greener practices:

• Use 2-MeTHF or EtOAc/DCM mixtures where feasible; prefer MeCN over chlorinated solvents if selectivity allows.
• Minimize excess oxidant; quantify by coulometry to avoid overuse.
• Recover ferrocene byproduct for reuse where practical.

Pharmaceutical Uses

No pharmacopeial grade or excipient role is specified for this item; refer to CoA/Spec Sheet. Ferrocenium hexafluorophosphate is primarily a laboratory reagent.

General, non-clinical context:

• Employed in process research and analytical development as a redox benchmark for nonaqueous electrochemical methods.
• Occasionally used to modulate oxidation states of organometallic catalysts during route scouting, enabling mechanistic probes without introducing coordinating anions.
• In materials/pharmaceutical analytics, ferrocene/ferrocenium couples serve as internal standards for evaluating solvent purity and electrochemical window in aprotic media.

Regulatory note: This reagent is not intended for use in human or veterinary drug products. Any consideration of GMP use would require establishing specifications for identity, assay, impurities (including fluoride release), residual solvents, and bioburden/endotoxin—none of which are specified for this catalog item.

Physical Properties

Only general/literature values are provided here for context; they are not item-specific specifications.

• Appearance: Often reported as a deep blue to blue-green crystalline solid (literature).
• Molecular weight: ~331.0 g/mol for C10H10FePF6 (literature calculation).
• Solubility (qualitative, literature):
  • Good: acetonitrile, nitromethane, nitrobenzene, dichloromethane, acetone.
  • Moderate/limited: lower alcohols; poorly soluble in nonpolar hydrocarbons.
  • Water: low to modest solubility; PF6− salts are generally poorly water-miscible.
• Density, melting point, decomposition temperature, refractive index, UV–Vis λmax, logP, pKa: Not specified for this item; refer to CoA/Spec Sheet.

Redox properties (literature, for reference):

• Standard potential E°(Fc+/Fc) is defined as 0.000 V by convention in nonaqueous electrochemistry; versus SCE it is typically ~+0.40 V in MeCN (literature). Ferrocenium PF6 functions as a one-electron outer-sphere oxidant, reverting to neutral ferrocene upon electron uptake.

Notes:

• Many PF6− salts show thermal decomposition and hydrolysis at elevated temperature or in strongly protic/acidic aqueous media. Handle under dry conditions to maintain integrity.

Quality and Grades

• Grade/purity: Not specified for this item; refer to CoA/Spec Sheet.

Guidance for evaluating this reagent (general for ferrocenium PF6):

• Assay and identity: Redox-active content can be assessed by coulometry or redox titration versus ferrocene. 1H NMR (paramagnetic broadening expected for Fc+) and UV–Vis can corroborate identity; elemental analysis supports PF6− stoichiometry.
• Counterion quality: Low levels of coordinating/halide anions (Cl−, Br−) are desirable to preserve outer-sphere behavior. ICP for trace metals and ion chromatography for anions are commonly used.
• Water content: Moisture reduces oxidizing strength and promotes hydrolysis; Karl Fischer water is often reported for high-purity lots. For this item: Not specified; refer to CoA/Spec Sheet.
• Residual solvents: Low boiling polar aprotic solvents (e.g., MeCN) are typical crystallization media—residual levels may be listed on the CoA.
• Stabilizers: Ferrocenium PF6 generally does not require stabilizers; maintaining dryness and inert atmosphere is critical. Any stabilizer present would be disclosed on the CoA; none are specified here.

Fit-for-use notes:

• For electrochemistry and doping studies, low water/halide content and consistent particle size improve reproducibility.
• For synthetic oxidation, assay-by-electron equivalents (e−/g) is the most practical performance metric.

Reaction and Applications

Ferrocenium hexafluorophosphate is a versatile, outer-sphere, one-electron oxidant that cleanly reduces to ferrocene, an easily separable, bench-stable byproduct.

Representative uses (literature/general):

• Single-electron transfer (SET) oxidations of electron-rich aromatics, enol ethers, sulfides, selenides, and tertiary amines to radical cations; subsequent trapping enables C–C or C–X bond formation.
• Oxidative activation of low-valent metal complexes (e.g., Pd(0)→Pd(II), Ni(0)→Ni(II)) under non-coordinating conditions to initiate catalytic cycles without introducing halides.
• Generation of carbocations from stabilized precursors via initial radical cation formation, promoting Friedel–Crafts-type transformations under mild conditions.
• Doping of conjugated polymers (e.g., PEDOT, polythiophenes) as a p-type dopant to enhance conductivity and tune work function in organic electronics.
• Redox mediator/standard in nonaqueous electrochemistry; Fc/Fc+ couple used for reference scale alignment and calibration.

Practical tips:

• Use 1.0 equivalent per electron for stoichiometric oxidations; add portionwise to control exotherm and color change (deep blue → orange ferrocene).
• Dry solvents/glassware rigorously; water quenches the oxidant and can hydrolyze PF6− under forcing conditions.
• Monitor by UV–Vis (decrease of Fc+ band, growth of Fc features) or cyclic voltammetry where applicable.
• Byproduct removal: ferrocene is neutral and often extractable into nonpolar solvents or removable by silica plug (orange band).

Reaction Conditions

The following are general literature guidelines; optimize for each substrate.

• Solvents: Dry MeCN, DCM, DCE, nitromethane. Avoid protic solvents and water.
• Stoichiometry: 1.0 equivalent per electron removed. Begin with 1.05–1.20 eq to compensate for trace moisture, then adjust based on assay.
• Temperature: 0 °C to room temperature typical; for sensitive substrates, −78 to 0 °C in DCM/MeCN mixtures. Elevated temperatures can accelerate side reactions and PF6− hydrolysis.
• Addition: Portionwise or syringe pump over 10–60 min to control exotherm and radical-cation concentration.
• Atmosphere: Inert (argon recommended). Degas solvents; dry glassware.
• Monitoring: TLC (watch for orange ferrocene), UV–Vis (decrease of Fc+ band, growth of Fc bands), or cyclic voltammetry for mechanistic studies.
• Workup: Quench residual oxidant with a mild electron donor (e.g., ferrocene or dilute ascorbate in a separate phase), extract ferrocene into hexanes, and purify product by silica gel (test stability first). Avoid aqueous strong base/acid.

Expected outcomes (literature ranges):

• Outer-sphere oxidations often proceed in minutes to a few hours at rt with 60–95% yields when substrates are suitably activated.
• Overoxidation/polymerization can occur with highly electron-rich arenes—dose control and low temperatures mitigate issues.

Safety and Handling

Safety data below are general best practices for oxidizing, moisture-sensitive PF6− salts and are not a substitute for the product-specific SDS.

• GHS classification, signal word, hazard statements, pictograms: Not specified for this item; refer to CoA/Spec Sheet and SDS.
• Principal hazards (general):
  • Strong one-electron oxidant; may cause exothermic reactions with reducing agents, organolithiums/Grignards, phosphines, sulfides, and easily oxidized organics.
  • PF6− salts can release HF upon severe hydrolysis/thermal decomposition—avoid strong acids, strong bases, and high heat in the presence of moisture.
  • Dust may be irritating; avoid inhalation and contact.
• PPE: Lab coat, safety glasses, appropriate chemically resistant gloves (e.g., nitrile). Use in a fume hood to avoid exposure to dust or vapors from reaction byproducts.
• Handling: Work quickly under dry, inert atmosphere (argon or nitrogen). Use anhydrous glassware/solvents. Avoid grinding with reactive metals or exposure to reducing agents.
• Incompatibilities: Reducing agents, strong bases, strong acids (promote PF6− hydrolysis), moisture, finely divided metals.
• First aid (general):
  • Skin/eye contact: Rinse with water for ≥15 min; remove contaminated clothing; seek medical attention if irritation persists.
  • Inhalation: Move to fresh air; seek medical attention if symptoms occur.
  • Ingestion: Rinse mouth; do not induce vomiting; seek medical attention.
• Defer to the SDS for authoritative and item-specific safety information.

Solvent Selection

Ferrocenium PF6 is ionic yet lipophilic due to PF6−; it dissolves best in polar, low-coordinating, aprotic media that stabilize outer-sphere electron transfer.

• Polarity class (general): Prefers medium-to-high polarity aprotic solvents.
• Recommended solvents (literature):
  • Excellent: acetonitrile (MeCN), nitromethane, nitrobenzene, dichloromethane (DCM), 1,2-dichloroethane (DCE), acetone.
  • Acceptable with care: DMF, DMSO (more coordinating; can alter redox thermodynamics/kinetics).
  • Generally poor: alkanes and ethers (solubility limited), water (low solubility; hydrolysis risk under harsh conditions).

Selection guidance:

• Kinetic outer-sphere oxidations: MeCN or DCM for fast, clean SET with minimal coordination.
• Polymer doping and film processing: MeCN or nitromethane for uniform wetting and volatility control.
• Organometallic oxidations: DCM/DCE preferred when avoiding ligand displacement; MeCN if a mildly coordinating environment is acceptable.

Quick comparison (general):

• MeCN: high dielectric, fast ET, easy removal, but absorbs water readily—dry before use.
• DCM/DCE: low nucleophilicity, good for sensitive substrates; lower dielectric than MeCN.
• Nitroalkanes: strong ion-solvation; higher bp aids controlled reactions but harder to remove.

Storage and Reconstitution

• Storage conditions (item-specific from Product Data): Store at 2–8 °C, Argon charged.
• Shipped in: Wet ice (item-specific).

General handling and stability notes:

• Keep container tightly closed under inert gas. Include desiccant in secondary containment to maintain dryness.
• Protect from moisture and prolonged light exposure. Avoid temperature excursions above ambient for extended periods.
• If preparing solutions: Use rigorously anhydrous solvents (e.g., MeCN, DCM). Sparge with argon and store solutions in sealed, inerted vials at 2–8 °C; prepare fresh when possible. Solution stability depends on solvent and impurities; verify by UV–Vis or a quick redox assay before critical use.
• Do not freeze aqueous mixtures (not recommended) and avoid aqueous stock solutions due to hydrolysis risk of PF6−.
• Disposal: Treat spent solutions and residues as oxidizing, fluorinated inorganic waste. Neutralize/quenched residues should be managed per institutional and regulatory guidance.

Lot-specific parameters (water content, assay, residual solvents) are not specified for this item; refer to CoA/Spec Sheet.

Structure and Identity

Ferrocenium hexafluorophosphate is a classic one-electron oxidant: the 18-electron metallocene cation [Fe(C5H5)2]+ paired with the weakly coordinating PF6− anion.

• SKU: F338461
• Product name: Ferrocenium hexafluorophosphate
• CAS: 11077-24-0; PubChem CID: 16212479
• InChIKey (as provided in Product Data): 273758
• SMILES: Not specified for this item; refer to CoA/Spec Sheet.

Structure description (general/literature):

• Cation: ferrocenium, [Fe(η5-C5H5)2]+, a sandwich complex with Fe center between two parallel cyclopentadienyl (Cp) rings; rings are typically staggered or eclipsed in solid state with overall D5h/D5d pseudo-symmetry. Formal Fe(III) d5, 17e? Note: ferrocenium is 17e, generated by one-electron oxidation of ferrocene.
• Anion: hexafluorophosphate, PF6−, octahedral around P with six equivalent F atoms; weakly coordinating, enhancing oxidizing power of the cation.

Identifiers and formula (literature values, for reference):

• Molecular formula (salt): C10H10FePF6 (literature)
• Molecular weight: ~331.0 g/mol (literature)

Key functional/structural features (general):

• Organometallic cation with delocalized positive charge over the Cp–Fe framework; aromatic Cp rings (10 π-electrons each) maintain hapticity in both Fc and Fc+ states.
• Counterion PF6− confers good crystallinity and low nucleophilicity; promotes solubility in polar aprotic solvents (e.g., MeCN, nitromethane) while limiting basicity and coordination.

Synthetic Utility

Key features enabling broad synthetic value:

• Functional group compatibility: As a weakly coordinating outer-sphere oxidant, ferrocenium PF6 often avoids direct substrate coordination, preserving delicate ligands or reactive centers. It is effective for oxidizing electron-rich aromatics, enol ethers, sulfides, selenides, and tertiary amines.
• Catalyst-state control: Cleanly oxidizes low-valent transition-metal complexes (Pd(0), Ni(0), Cu(I), Ru(II) in some systems) to higher oxidation states to initiate or modulate catalytic cycles without halide introduction—useful in cross-coupling and C–H activation studies.
• Radical-cation pathways: Facilitates SET to generate radical cations that can undergo fragmentation, rearrangement, or nucleophile capture, enabling C–C and C–X bond formations under mild conditions.
• Polymer and materials chemistry: Acts as a p-dopant for conjugated polymers and small molecules, increasing conductivity and tuning Fermi level/work function in organic electronic devices.

Practical synthetic notes:

• Byproduct ferrocene is benign and easily separated (orange, neutral), simplifying workup relative to heavy-metal oxidants.
• PF6− minimizes nucleophilic interception of cationic intermediates; when more coordinating environments are desired, switch counterion (e.g., BF4−) or solvent accordingly.
• Control reaction temperature and dosing to avoid overoxidation; consider electroanalytical pre-screening to map redox windows.

Target Specificity

Not applicable. This product is a small-molecule inorganic/organometallic reagent, not a biological targeting reagent. No antigen/epitope specificity, clone, isotype, or species reactivity applies.