A review on the halodefluorination of aliphatic fluorides

Synthesis ◽  
2021 ◽  
Author(s):  
Richa Gupta ◽  
Rowan Young
Keyword(s):  
Metal Halide ◽  
Catalytic Process ◽  
Metal Halides ◽  
Reaction Step ◽  
Group 13 ◽  
Cascade Processes

Halodefluorination of alkylfluorides using Group 13 metal halides has been known for quite some time (first reported by Newman in 1938) and is often utilised in its crude stoichiometric form to substitute fluorine with heavier halogens. However, recently halodefluorination has undergone many developments. The reaction can be effected with a range of metal halide sources (including s-block, f-block and p-block metals), and has been developed into a catalytic process. Further, methods for monoselective halodefluorination in polyfluorocarbons have been developed allowing exchange of only a single fluorine with a heavier halogen. The reaction has also found use in cascade processes where the final product may not even contain halide, yet the conversion of fluorine to more reactive halogens is a pivotal reaction step in the cascade. This review provides a summary of the developments in the reaction since its inception until now.

Versatile structures of group 13 metal halide complexes with 4,4′-bipy: from 1D coordination polymers to 2D and 3D metal–organic frameworks

2015 ◽  
Vol 44 (47) ◽  
pp. 20648-20658 ◽  
Author(s):  
Tatiana N. Sevastianova ◽  
Michael Bodensteiner ◽  
Albina F. Maulieva ◽  
Elena I. Davydova ◽  
Alexander V. Virovets ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Metal Organic Frameworks ◽  
Metal Halide ◽  
Metal Halides ◽  
Group 13 ◽  
Metal Organic ◽  
Halide Complexes ◽  
2D And 3D

The nature of the group 13 metal halides strongly affects the structure of their complexes with 4,4′-bipy.

Crystal structures and thermal behavior of complexes of group 13 metal halides with pyridine-type ligands

2015 ◽  
Vol 64 (11) ◽  
pp. 2523-2535 ◽  
Author(s):  
T. N. Sevastianova ◽  
E. I. Davydova ◽  
I. V. Kazakov ◽  
A. Yu. Timoshkin
Keyword(s):  
Thermal Behavior ◽  
Crystal Structures ◽  
Metal Halides ◽  
Group 13

Investigation of mesitylene-solvated group 13 mixed-metal halides: syntheses and crystal structures of bis(1,3,5-trimethylbenzene)gallium(I) tetrachlorido- and tetrabromidoaluminate(III) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III). Variation of the gallium-π-arene bond strength

2019 ◽  
Vol 74 (10) ◽  
pp. 773-782
Author(s):  
Luca Küppers ◽  
Walter Frank
Keyword(s):  
Structure Type ◽  
Monoclinic Space Group ◽  
Metal Halides ◽  
Group 13 ◽  
Space Group ◽  
X Ray ◽  
Mixed Metal ◽  
Main Group Metal ◽  
Arene Complex ◽  
Polymeric Chains

AbstractBis(1,3,5-trimethylbenzene)gallium(I) tetra­chloridoaluminate(III), [(1,3,5-(CH3)3C6H3)2Ga][AlCl4] (1), bis(1,3,5-trimethylbenzene)gallium(I) tetrabromido­aluminate(III), [(1,3,5-(CH3)3C6H3)2Ga][AlBr4] (2) and (1,3,5-trimethylbenzene)gallium(I) tetraiodidoaluminate(III), [1,3,5-(CH3)3C6H3Ga][AlI4] (3) were synthesized from the corresponding subvalent GaI/AlIII mixed metal halides and characterized via C,H analysis, Raman spectroscopy, X-ray powder diffraction and X-ray single crystal diffraction. Compound 1 crystallizes in the noncentrosymmetric monoclinic space group Cc isotypic to [(1,3,5-(CH3)3C6H3)2Ga][GaCl4]. For 2 and 3 the monoclinic space group P21/n is found, however, they are neither isotypic nor homotypic. While 2 is isotypic to [(1,3,5-(CH3)3C6H3)2In][InBr4], 3 establishes a new structure type. In the solids of all three title compounds coordination polymeric chains are found, in 1 and 2 built up from bis(arene)-coordinated, in 3 from mono(arene)-coordinated Ga+ ions and the corresponding AlX4− anions in a 1κCl:2κCl′ (1), 1κCl,Cl′:2κCl″ (2) or 1κCl,Cl′:2κCl″:3κCl‴ (3) bridging mode. Taking into account the weaker coordinating character of the AlCl4− as compared to the AlBr4− anion, in line with expectations the number of gallium halogen contacts is increased and the strength of the π-arene bonding is reduced in the bromide 2 as compared to the chloride 1. Finally, with the even more strongly coordinating AlI4− anion the arene coordination is limited to one molecule. Considering mesitylene complexes of gallium, the formation of a mono(arene) complex is unprecedented and even considering group 13 elements in general, the formation of a mono(mesitylene) complex like 3 is unusual. Furthermore, compound 3 is the first structurally characterized arene solvate of a main group metal tetraiodidometallate.

scholarly journals Organic Metal Halide Hybrids: Bulk Assembly of Corrugated 1D Metal Halides with Broadband Yellow Emission (Advanced Optical Materials 6/2019)

2019 ◽  
Vol 7 (6) ◽  
pp. 1970021
Author(s):  
Haoran Lin ◽  
Chenkun Zhou ◽  
Jennifer Neu ◽  
Yan Zhou ◽  
Dan Han ◽  
...  
Keyword(s):  
Optical Materials ◽  
Metal Halide ◽  
Yellow Emission ◽  
Organic Metal ◽  
Metal Halides

Masking of Lewis acidity trends in the solid-state structures of trichlorido- and tribromido(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)gallium(III)

2014 ◽  
Vol 70 (3) ◽  
pp. 312-314 ◽  
Author(s):  
Igor V. Kazakov ◽  
Michael Bodensteiner ◽  
Alexey Y. Timoshkin
Keyword(s):  
Solid State ◽  
Experimental Error ◽  
Octahedral Geometry ◽  
Molecular Structures ◽  
Lewis Acidity ◽  
Metal Halides ◽  
Group 13 ◽  
Monodentate Ligands ◽  
Solid State Structures ◽  
Bromide Complex

The molecular structures of trichlorido(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)gallium(III), [GaCl3(C15H11N3)], and tribromido(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)gallium(III), [GaBr3(C15H11N3)], are isostructural, with the GaIIIatom displaying an octahedral geometry. It is shown that the Ga—N distances in the two complexes are the same within experimental error, in contrast to expected bond lengthening in the bromide complex due to the lower Lewis acidity of GaBr3. Thus, masking of the Lewis acidity trends in the solid state is observed not only for complexes of group 13 metal halides with monodentate ligands but for complexes with the polydentate 2,2′:6′,2′′-terpyridine donor as well.

Large-scale facile-synthesis and bistable emissions of one-dimensional organic-inorganic C4H14N2PbBr4 metal halide crystals with bipolaronic states

2021 ◽  
Author(s):  
hui peng ◽  
ye tian ◽  
xinxin wang ◽  
shangfei yao ◽  
tao huang ◽  
...  
Keyword(s):  
Physical Properties ◽  
Mechanochemical Synthesis ◽  
Potential Application ◽  
Large Scale ◽  
Metal Halide ◽  
Metal Halides ◽  
Facile Synthesis ◽  
One Dimensional ◽  
Low Dimensional

Low-dimensional metal halides have attracted much attention because of its excellent physical properties and potential application in optoelectronic field. Herein, we developed a novel facile method based on mechanochemical synthesis...

Ring and cage compounds from complexes of group 13 metal halides with ethylenediamine: Experiment and theory

2007 ◽  
Vol 692 (13) ◽  
pp. 2822-2831 ◽  
Author(s):  
C. Trinh ◽  
A.Y. Timoshkin ◽  
S.M. Matveev ◽  
A.D. Misharev
Keyword(s):  
Metal Halides ◽  
Cage Compounds ◽  
Group 13

The Protective Action of Some Antioxidants II. The Metal Halide Compounds of Some Protective Agents against Aging, with Special Reference to Aldol-Alpha-Naphthylamine

1931 ◽  
Vol 4 (2) ◽  
pp. 239-247
Author(s):  
F. Kirchhof
Keyword(s):  
Heavy Metal ◽  
Ferric Chloride ◽  
Complex Compounds ◽  
Cupric Chloride ◽  
Metal Halide ◽  
Hydrocyanic Acid ◽  
Stable Complex ◽  
Metal Halides ◽  
Protective Agents ◽  
Complex Metal

Abstract The results described in the present paper can be summarized as follows: 1. Certain antioxidants containing nitrogen, like aldol-α-naphthylamine and Stabilite Alba, give in alcoholic solution with higher halides of certain metals, especially those of iron and copper, unstable intense blue-violet as well as stable carmine-red colorations, which may be regarded as more or less stable complex compounds of these antioxidants. A series of other heavy metal halides of which similar behavior would be expected (for example, SnCl4, CoCl3, etc.) give no color reactions of this kind. 2. Both the chemical and the optical behavior of these colored solutions indicate that they contain complexes of ferric chloride and cupric chloride groups attached to tertiary nitrogen, as in the haemin of blood pigment. 3. Of the antioxidants studied here, aldol-α-naphthylamine reacts quickest with the metal halides named above, Agerite the slowest and Stabilite Alba somewhere between the two. The reaction with cupric chloride occurs in every case much more rapidly than that with ferric chloride. It is obvious that this behavior might be utilized to distinguish analytically small quantities of these substances. 4. The complex metal halide compounds show strong oxygen-transporting action, as does the haemin of the blood, which contains iron. This is many times greater with the compounds of antioxidants which contain copper than with those which contain iron compounds, and this agrees with the similar behavior of compounds of these metals with rubber, as has long been known. 5. Since the antioxidants are oxidized in the course of time, as the result of autoöxidation, they protect an autoöxidizable substance like rubber only so long as they are not rendered inactive. Since traces of soluble heavy metal compounds, especially of iron, are invariably present in rubber compounding ingredients, it can be understood why rubber mixtures containing protective agents are more or less strongly and more or less rapidly discolored as a result of the formation of dark-colored metal complex compounds and their oxidation products. 6. Finally it was possible to show that the complex metal halide compounds of the antioxidants studied are remarkably sensitive toward certain catalytic poisons such as hydrocyanic acid, in quite an analogous fashion to known biological oxygen carriers. It is entirely possible that this phenomenon may also be of significance in the use of protective agents in technical rubber mixtures.

Oxidative Addition of Group 13 and 14 Metal Halides and Alkyls to Ga(DDP) (DDP = Bulky Bisimidinate)

2008 ◽  
Vol 47 (16) ◽  
pp. 7279-7285 ◽  
Author(s):  
Andreas Kempter ◽  
Christian Gemel ◽  
Roland A. Fischer
Keyword(s):  
Oxidative Addition ◽  
Metal Halides ◽  
Group 13

White-Light Defect Emission and Enhanced Photoluminescence Efficiency in 0D Indium-Based Metal Halide

2022 ◽  
Author(s):  
Qidi Ran ◽  
Yan Zhang ◽  
Jun Yang ◽  
Rongxing He ◽  
Lei Zhou ◽  
...  
Keyword(s):  
White Light ◽  
Electronic States ◽  
Luminescent Properties ◽  
Metal Halide ◽  
Metal Halides ◽  
Defect Emission ◽  
Enhanced Photoluminescence ◽  
Low Dimensional ◽  
Confined Structure ◽  
Photoluminescence Efficiency

Low-dimensional ns2-metal halide compounds with confined structure and localized electronic states have received considerable attention for their superior luminescent properties. While the intrigue photophysical dynamics of metal halides without ns2...

Sign in / Sign up

Export Citation Format

Share Document