32760-80-8

Usage

Uses

Used in Coordination Chemistry:
Iron(1+), (.eta.5-2,4-cyclopentadien-1-yl)(1,2,3,4,5,6-.eta.)-(1-methylethyl)benzene-, hexafluorophosphate(1-) is used as a precursor in coordination chemistry for the synthesis of various iron-containing complexes. Its ability to donate the iron(1+) cation makes it a versatile building block for creating new coordination compounds with potential applications in catalysis, materials science, and other areas.
Used in Organometallic Synthesis:
In organometallic synthesis, Iron(1+), (.eta.5-2,4-cyclopentadien-1-yl)(1,2,3,4,5,6-.eta.)-(1-methylethyl)benzene-, hexafluorophosphate(1-) is utilized as a reagent to produce organometallic compounds. These compounds are important in various chemical transformations and can be used as catalysts, ligands, or precursors for the synthesis of more complex organometallic species.
Used in Catalyst Preparation:
Iron(1+), (.eta.5-2,4-cyclopentadien-1-yl)(1,2,3,4,5,6-.eta.)-(1-methylethyl)benzene-, hexafluorophosphate(1-) is used as a catalyst precursor in various chemical reactions. The iron(1+) cation can be incorporated into catalytic systems, where it can facilitate transformations such as oxidation, reduction, and coupling reactions. Its use in catalyst preparation allows for the development of more efficient and selective catalytic processes.
Used in Materials Science:
In the field of materials science, Iron(1+), (.eta.5-2,4-cyclopentadien-1-yl)(1,2,3,4,5,6-.eta.)-(1-methylethyl)benzene-, hexafluorophosphate(1-) can be employed in the development of new materials with unique properties. The incorporation of iron(1+) into various structures can lead to materials with enhanced magnetic, electronic, or optical properties, making them suitable for applications in sensors, electronic devices, or energy storage systems.
Used in Pharmaceutical and Medicinal Chemistry:
Although not explicitly mentioned in the provided materials, it is worth noting that organometallic compounds, including those containing iron, have been explored for their potential applications in pharmaceutical and medicinal chemistry. Iron(1+), (.eta.5-2,4-cyclopentadien-1-yl)(1,2,3,4,5,6-.eta.)-(1-methylethyl)benzene-, hexafluorophosphate(1-) could potentially be used as a starting material for the synthesis of bioactive organometallic compounds with therapeutic properties.

InChI:InChI=1/C9H12.C6H7.6FH.Fe.P/c1-8(2)9-6-4-3-5-7-9;1-2-4-6-5-3-1;;;;;;;;/h3-8H,1-2H3;1-5H,6H2;6*1H;;/q;-1;;;;;;;+2;+5/p-6

Synthetic route

hexafluorophosphoric acid + {(Cp)iron(II)(η5-C6H5(isopropyl)O)}2 → (η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8)

Conditions	Yield
In diethyl ether byproducts: H2O2; The dimeric peroxide complex is hydrolyzed by HPF6 at -80°C under dry N2.; characterization by (1)H NMR;	50%

sodium hexaflorophosphate + {(Cp)iron(I)(η6-isopropylbenzene)} (98162-09-5) → sodium peroxide + (η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8)

Conditions	Yield
With oxygen In tetrahydrofuran addn. of O2 at -80°C under dry N2;

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) + α-cyclodextrin (10016-20-3, 123880-20-6, 150521-49-6) → (η5-cyclopentadienyl)iron(II)(η6-cumene) hexafluorophosphate*2α-cyclodextrin*13H2O

Conditions	Yield
In water molar ratio cyclodextrin:metal=2.2:1 (80°C, several min.); filtration, slow cooling to room temp. (pptn.), filtration, washing (H2O, EtOH), drying (vac.); elem. anal.;	97%

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) + β-cyclodextrin (7585-39-9, 130322-66-6, 130322-68-8) → (η5-cyclopentadienyl)iron(II)(η6-cumene) hexafluorophosphate*2β-cyclodextrin*8H2O

Conditions	Yield
In water molar ratio cyclodextrin:metal=2.2:1 (80°C, several min.); filtration, slow cooling to room temp. (pptn.), filtration, washing (H2O, EtOH), drying (vac.); elem. anal.;	77%

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) + acrylic acid methyl ester (292638-85-8) → {(C5H5)Fe(C6H5C(CH3)2(CH2)2CO2CH3)}(1+)*PF6(1-)={(C5H5)Fe(C6H5C(CH3)2(CH2)2CO2CH3)}PF6

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran under N2, to THF added Fe complex and t-BuOK at 25°C, stirred for 15 min, CH2CHCO2Me in THF added dropwise during 5-7 min, after addnl. 5 min treated with either 1% HCl or 5% aq. NH4Cl; rotary evapd., dissolved in CH2Cl2, dried over MgSO4, concd., ether added, crystals sepd., chromd. (Al2O3, CH2Cl2); elem. anal.;	76%

1-chloro-2,3,4,5-tetraethylphosphole (312920-30-2) + (η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) → tetraethyl-1-monophosphaferrocene (312920-34-6)

Conditions	Yield
With Li In tetrahydrofuran stirred for 1 h, Fe-complex added, stirred under N2 for 30 min at 35°C; solvent evpd., pptd. with hexane; elem. anal.;	71%

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) + acrylonitrile (107-13-1) → {(C5H5)Fe(C6H5C(CH3)2(CH2)2CN)}(1+)*PF6(1-)={(C5H5)Fe(C6H5C(CH3)2(CH2)2CN)}PF6

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran under N2, to THF added Fe complex and t-BuOK at 25°C, stirred for 15 min, CH2CHCN in THF added dropwise during 5-7 min, after addnl. 5 min treated with either 1% HCl or 5% aq. NH4Cl; rotary evapd., dissolved in CH2Cl2, dried over MgSO4, concd., ether added, crystals sepd., chromd. (Al2O3, CH2Cl2); elem. anal.;	65%

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) + K(1+)*(CH3)4C5P(CH)2(CCH3)2(1-)=K(PC15H20) → 3,4-dimethyl-1-phosphaferrocene + (C5H5)Fe(PC4H(CH3)2C5H(CH3)4) (391868-31-8, 391902-50-4)

Conditions	Yield
In tetrahydrofuran potassium P-cyclopentadienide was heated at 140°C in THF for 16 h, Fe complex was added at 25°C and stirred for 10 h; purification by chromy. on silica (90:10 hexane-CH2Cl2); elem. anal.;	A n/a B 41%

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) → {(Cp)iron(I)(η6-isopropylbenzene)} (98162-09-5)

Conditions	Yield
With Na#Hg In tetrahydrofuran at -20°C; filtered;

(η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) → {(Cp)iron(II)(η5-C6H5(isopropyl)O)}2

Conditions	Yield
With sodium amalgam; oxygen In 1,2-dimethoxyethane; toluene The (CpFe(II))PF6 complex in DME is stirred with Na/Hg for 2 h at -20°C under an atmosphere of dry N2, the yielding green neutral complex reacts at -80°C with O2 in toluene, color change of the soln. from green to light orange.; detected by IR;
With sodium amalgam; oxygen In 1,2-dimethoxyethane; pentane The (CpFe(II))PF6 complex in DME is stirred with Na/Hg for 2 h at -20°C under an atmosphere of dry N2, the yielding green neutral complex reacts at -80°C with O2 in pentane.; the soln. is concd., crystn. (pentane), a mixture of isomers of dimeric peroxide complex in 81 % yield is obtained, investigated by (1)H NMR, (13)C NMR, elem. anal.;

1,10-Phenanthroline (66-71-7) + (η6-cumene)(η5-cyclopentadienyl)iron hexafluorophosphate (32760-80-8) → ferroin (47836-89-5, 14708-99-7, 24324-38-7)

Conditions	Yield
In acetone Kinetics; byproducts: isopropylbenzene, C5H5(1-); Irradiation (UV/VIS); at 355-683 nm;
In dichloromethane Kinetics; byproducts: isopropylbenzene, C5H5(1-); Irradiation (UV/VIS); at 355-683 nm;
In further solvent(s) Kinetics; byproducts: isopropylbenzene, C5H5(1-); Irradiation (UV/VIS); at 355-683 nm in 1,2-dichloroethane;

Upstream product

• 98162-09-5 {(Cp)iron(I)(η6-isopropylbenzene)} 

Relevant academic research and scientific papers

How dioxygen activates C-H bonds of simple arenes in unstable CpFeI(arene) complexes and the versatile reactivity of superoxide anion generated from dioxygen and organoiron electron reservoirs

The reactivity of O2.- generated in inert solvents and ethers from dioxygen and electron reservoirs such as CpFeI(arene) complexes has been examined with the aim of activating benzylic C-H bonds in simple arenes coordinated to CpFeI. The C-H activation by O2 in pentane, THF, or DME, known for C5R6FeI(C6R′6) (R and R′ = alkyls), is investigated for unstable CpFeI(arene) complexes with one to six methyl groups on the arene ligand. A dramatic salt effect is found when the reactions are carried out in THF; in the presence of Na+X-, the formation of yellow diagmagnetic salts [CpFe(arene)]+X- and of 1/2 mol of Na2O2 is general; it is quantitative with X- = PF6- upon reaction with 1/2 mol of O2 at -80°C. When Na+X- is removed, the unstable CpFeII(η5-benzyl) complexes are obtained in high yield and characterized by the downfield resonance (140 ppm) observed in the 13C{1H} spectra for the ring carbon bound to the exocyclic double bond; they can be alkylated or functionalized in situ at -50°C with CH3I or PhCOCl. Primary, secondary, and tertiary C-H bonds can be activated in this way by O2 in the 19-electron CpFeI(arene) complexes. The rapid H-atom abstraction from methyl and ethyl substitutents at -80°C is an outer-sphere electron transfer to dioxygen followed by deprotonation by superoxide anion, the latter process being inhibited by the salt effect (Na+). The formation of dimeric peroxides is a general phenomenon in the reactions of 1/2 mol of O2 in pentane or toluene with CpFeI complexes of arenes such as C6H6 or 1,3,5-t-Bu3C6H3 which do not bear benzylic hydrogens. The competition between formation of a dimeric peroxide and benzylic H abstraction is exemplified by the behavior of CpFeI(i-PrC6H5); reaction of O2 with the latter in toluene gives the dimeric peroxide as the kinetic product (-80°C), transformed into the thermodynamic H abstraction product at -17°C. The salt effect in THF with M+X- (M+ = n-Bu4N+, K+, Na+, X- = PF6-, BF4-, F-) also inhibits the formation of dimeric peroxide, and the salts [CpFe(arene)]PF6 and Na2O2 are formed instead of the dimer. The salt effect is all the more important in the series M+X- as the size of the cation M+ decreases and as that of the anion X- increases. In all the reactions, formation of superoxide anion in ion pairs is the first step and its versatile reactivity (proton abstraction, nucleophilic addition, reduction or dismutation) accounts for the variety of reactions observed.