335. The reaction of fluorine with the oxides and oxy-compounds of manganes and rhenium

Aynsley, E. E.; Peacock, R. D.; Robinson, Percy Lucock

doi:10.1039/jr9500001622

Cited by 24 publications

(13 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Under these conditions, the spinel Mn 3 O 4 phase forms. These observations are validated by data reporting that manganese oxides already react with F 2 diluted with N 2 at 100 °C to produce MnF 3 and minor amounts of MnF 2 , that is the fluoride phases are thermodynamically more stable than Mn oxides 21…”

Section: Resultssupporting

confidence: 65%

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)₂•tmeda

Lipani

Catalano

Rossi

et al. 2013

Chemical Vapor Deposition

View full text Add to dashboard Cite

The complex, Mn(hfa) 2 tmeda [(H-hfa ¼ 1, 1,1,5,5,5-hexafluoro-2,4-pentandione, tmeda ¼ N,N,N 0 ,N 0 -tetramethylethylendiamine)], is synthesized in a single-step reaction and characterized by elemental analysis, thermal analysis, and infrared (IR) spectroscopy. The solid-state crystal structure of Mn(hfa) 2 tmeda provides evidence of a mononuclear structure. The thermal analyses show that the complex is thermally stable and can be evaporated to leave less than 2% residue. The complex properties are compared with the first generation, commercially available Mn II and Mn III precursors, Mn(acac) 2 (Hacac ¼ acetylacetone) and Mn(tmhd) 3 (Htmhd ¼ 2,2,6,6-tetramethyl-3,5-heptanedione), respectively. Mn(hfa) 2 tmeda represents the first example of manganese(II) precursor that can be used in the liquid phase without decomposition, thus providing constant evaporation rates, even for long deposition times. It is successfully applied to the reduced-pressure, metal-organic (MO)CVD of the Mn 3 O 4 phase.[**] The authors thank the MIUR for the financial support within the PRIN 2009 N. 20097 Â 44S7_002 (Hybrid materials based on lanthanide complexes for sensing applications) and the FIRB ITALNANONET RBPR05JH2P project. 22

show abstract

Section: Resultssupporting

confidence: 65%

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)₂•tmeda

Lipani

Catalano

Rossi

et al. 2013

Chemical Vapor Deposition

View full text Add to dashboard Cite

show abstract

“…The present synthesis provides ReO 2 F 3 in quantitative yield as a stable, white, microcrystalline solid which is essentially insoluble in anhydrous HF and has a melting point (113−116 °C) which is consistent with the observations of Stevie and Sunder, who reported an almost white solid and similar melting point (115 °C). The purity of this material is significantly higher than that reported by Peacock et al, who described ReO 2 F 3 as a pale yellow solid melting at 90 °C. Unlike TcO 2 F 3 , ReO 2 F 3 is stable in Pyrex glass and in CH 3 CN solutions at room temperature; however, CH 3 CN solutions of ReO 2 F 3 produce charring at −40 °C in the presence of [N(CH 3 ) 4 ][F], and ReO 2 F 3 solutions in CH 2 Cl 2 undergo rapid decomposition at room temperature to give blue solutions, typical of Re(VI) species.…”

Section: Resultsmentioning

confidence: 49%

“…Synthesis of ReO 2 F 3 . Previous syntheses of ReO 2 F 3 have involved direct fluorination of Re 2 O 7 or ReO 2 at elevated temperatures, followed by separation of the products by vacuum sublimation. ,, The heptoxide has also been fluorinated using BrF 3 , but the tendency of the Lewis acid ReO 2 F 3 to form adducts with excess BrF 3 made complete removal of this reagent difficult …”

Section: Resultsmentioning

confidence: 99%

Lewis Acid Behavior of ReO₂F₃: Synthesis of (ReO₂F₃)_∞, ReO₂F₄^-, Re₂O₄F₇^-, Re₃O₆F₁₀^-, and ReO₂F₃(CH₃CN) and Study by NMR Spectroscopy, Raman Spectroscopy, and Density Functional Theory Calculations; and X-ray Structures of [Li][ReO₂F₄], [K][Re₂O₄F₇
Casteel
¹
,
Dixon
²
,
LeBlond
³

et al. 1999
Inorg. Chem.
33
15
71
0
View full text Add to dashboard Cite

The reaction of Re2O7 with XeF6 in anhydrous HF provides a convenient route to high-purity ReO2F3. The fluoride acceptor and Lewis base properties of ReO2F3 have been investigated leading to the formation of [M][ReO2F4] [M = Li, Na, Cs, N(CH3)4], [K][Re2O4F7], [K][Re2O4F7]·2ReO2F3, [Cs][Re3O6F10], and ReO2F3(CH3CN). The ReO2F4 -, Re2O4F7 -, and Re3O6F10 - anions and the ReO2F3(CH3CN) adduct have been characterized in the solid state by Raman spectroscopy, and the structures [Li][ReO2F4], [K][Re2O4F7], [K][Re2O4F7]·2ReO2F3, [Cs][Re3O6F10], and ReO3F(CH3CN)2·CH3CN have been determined by X-ray crystallography. [Li][ReO2F4] crystallizes in the tetragonal system, space group P4̄21 m, with a = 4.727(3) Å, c = 8.880(7) Å, V = 198.4(7) Å3, and Z = 2 at 24 °C, R 1 = 0.0378, and wR 2 = 0.1029. [K][Re2O4F7] crystallizes in the monoclinic system, space group P2/n, with a = 5.4990(11) Å, b = 5.1530(10) Å, c = 14.753(3) Å, β = 95.68°, V = 415.99(14) Å3, and Z = 2 at 20 °C, R 1 = 0.0473, and wR 2 = 0.1200. [K][Re2O4F7]·2ReO2F3 crystallizes in the monoclinic system, space group C2, with a = 27.32(2) Å, b = 5.274(5) Å, c = 5.355(3) Å, β = 99.53(4)°, V = 760.9(11) Å3, and Z = 2 at −60 °C, R 1 = 0.0238, and wR 2 = 0.0645. [Cs][Re3O6F10] crystallizes in the triclinic system, space group P1̄, with a = 7.011(1) Å, b = 9.773(2) Å, c = 10.331(2) Å, α = 113.73(1)°, β = 91.05(2)°, γ = 92.42(2)°, V = 647.4(2) Å3, and Z = 2 at −118 °C, R 1 = 0.0522, and wR 2 = 0.0529. ReO3F(CH3CN)·CH3CN crystallizes in the orthorhombic system, space group Pnma, with a = 9.138(3) Å, b = 12.518(5) Å, V = 1045.4(7) Å3, and Z = 4 at −63 °C, R 1 = 0.0198, and wR 2 = 0.0605. The structure of ReO2F4 - consists of a cis-dioxo arrangement of Re−O double bonds in which the Re−F bonds trans to the oxygen atoms are significantly lengthened as a result of the trans influence of the oxygens. The Re2O4F7 - and Re3O6F10 - anions and polymeric ReO2F3 are open chains containing fluorine-bridged ReO2F4 units in which each pair of Re−O bonds are cis to each other and the fluorine bridges are trans to oxygens. The trans influence of the oxygens is manifested by elongated terminal Re−F bonds trans to Re−O bonds as in ReO2F4 - and by the occurrence of both fluorine bridges trans to Re−O bonds. Fluorine-19 NMR spectra show that ReO2F4 -, Re2O4F7 -, and ReO2F3(CH3CN) have cis-dioxo arrangements in CH3CN solution. Density functional theory calculations at the local and nonlocal levels confirm that the cis-dioxo isomers of ReO2F4 - and ReO2F3(CH3CN), where CH3CN is bonded trans to an oxygen, are the energy-minimized structures. The adduct ReO3F(CH3CN)2·CH3CN was obtained by hydrolysis of ReO2F3(CH3CN), and was shown by X-ray crystallography to have a facial arrangement of oxygen atoms on rhenium.

show abstract

“…The simplest compound in this class, ReO 2 F 3 , was first prepared by fluorination of KReO 4 under controlled temperature (100 °C) where the contamination of ReOF 5 can be reduced to 1/10 155c…”

Section: The L3reo2 Compounds and Derivativesmentioning

confidence: 99%

Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications

1997

View full text Add to dashboard Cite

ContentsI. Introduction 3197 II. LReO 3 Compounds and Derivatives 3199 A. Inorganic XReO 3 Compounds and Derivatives 3199 1. Dirhenium Heptaoxide, Re 2 O 7 , and Derivatives 3199 2. Halides and Pseudohalides of Type XReO 3 and Their Adducts 3200 3. R 3 EOReO 3 Compounds and Their Adducts (E ) C, Si, Sn, Ge, Sn, Pb) 3202 4. The Amido R 2 NReO 3 , the Phosphiniminato Complexes, and Their Adducts 3204 5. The Carboxylato Complexes (RCOO)-ReO 3 and Their Adducts 3204 6. The [L 3 ReO 3 ] + and [L 3 ReO 3 ] Complexes 3205 7. Miscellaneous Inorganic LReO 3 Derivatives 3206 8. Structural and Spectroscopic Characterization 3206 9. Reactions of Re 2 O 7 and XReO 3 Compounds 3208 B. Organic RReO 3 Compounds and Derivatives 3209 1. The Alkyl RReO 3 Derivatives 3209 2. The Methyl(vinyl)ReO 3 Complex 3212 3. Allyl, Benzyl, and Pseudoallylic Compounds 3212 4. The Alkinyl RReO 3 Derivatives 3212 5. The Aryl Derivatives 3213 6. The Cyclopentadienyl Derivatives 3213 7. The Indenyl Derivative 3214 8. Structural and Spectroscopic Characterization 3215 9. Reactions of Organic RReO 3 Compounds 3220 10. Applications 3223 III. The L 3 ReO 2 Compounds and Derivatives 3230 A. Inorganic X 3 ReO 2 Derivatives 3230 B. Organic and Mixed Derivatives 3231 IV. The L 4 Re 2 O 5 Compounds and Derivatives 3234 V. The L 5 ReO Compounds and Derivatives 3234 VI. The Re(VII) Imido Compounds and Derivatives 3234 A. The Inorganic XRe(NR) 3 Derivatives 3235 B. The Organic RRe(NR) 3 Derivatives 3236 C. The Inorganic X 3 Re(NR) 2 Derivatives 3236 D. The Organic R 3 Re(NR) 2 Derivatives 3237 E. Miscellaneous Polynuclear and Mixed Imido and Oxo−Imido Derivatives 3238 F. The X 5 Re(NR) Derivatives 3238 G. Reactions of XRe(NR) 3 Complexes 3238 H. Reactions of X 3 Re(NR) 2 and Derivatives 3239 1. The Imido−Alkyne XR(NAr) x (η 2 -C 2 R 2 ) 3-x Complexes 3239 2. The Imido−Alkylidene and Imido−Alkylidyne Complexes 3240 I. Structural Studies 3241 VII. Conclusions 3243 VIII. Abbreviations 3243 IX. Acknowledgments 3243 X. References 3243 3197

show abstract

335. The reaction of fluorine with the oxides and oxy-compounds of manganes and rhenium

Cited by 24 publications

References 0 publications

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)₂•tmeda

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)₂•tmeda

Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications

Contact Info

Product

Resources

About

335. The reaction of fluorine with the oxides and oxy-compounds of manganes and rhenium

Cited by 24 publications

References 0 publications

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)2•tmeda

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)2•tmeda

Rhenium(VII) Oxo and Imido Complexes: Synthesis, Structures, and Applications

Contact Info

Product

Resources

About

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)₂•tmeda

A Novel Manganese(II) MOCVD Precursor: Synthesis, Characterization, and Mass Transport Properties of Mn(hfa)₂•tmeda