Английская Википедия:Indium halides

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Шаблон:Short description There are three sets of Indium halides, the trihalides, the monohalides, and several intermediate halides. In the monohalides the oxidation state of indium is +1 and their proper names are indium(I) fluoride, indium(I) chloride, indium(I) bromide and indium(I) iodide.

The intermediate halides contain indium with oxidation states, +1, +2 and +3.

Indium trihalides

In all of the trihalides the oxidation state of indium is +3, and their proper names are indium(III) fluoride, indium(III) chloride, indium(III) bromide, and indium(III) iodide. The trihalides are Lewis acidic. Indium trichloride is a starting point in the production of trimethylindium which is used in the semiconductor industry.

Indium(III) fluoride

InF₃ is a white solid, m.p. 1170 °C. Its structure contains 6 coordinate indium.

Indium(III) chloride

InCl₃ is a white solid, m.p. 586 °C. It is obtained by oxidation of indium with chlorine. It is isostructural with AlCl₃.

Indium(III) bromide

InBr₃ is a pale yellow solid, m.p. 435 °C. It is isostructural with AlCl₃. It is prepared by combining the elements. InBr₃ finds some use in organic synthesis as a water tolerant Lewis acid.

Indium(III) iodide

Файл:Indium(III)-iodide-3D-balls.png

Ball-and-stick model of the In₂I₆ molecule

InI₃ is a yellow solid. It is obtained by evaporation of a solution of indium in HI. Distinct yellow and a red forms are known. The red form undergoes a transition to the yellow at 57 °C. The structure of the red form has not been determined by X-ray crystallography, however spectroscopic evidence indicates that indium may be six coordinate. The yellow form consists of In₂I₆ with 4 coordinate indium centres. It is used as an "iodide getter" in the Cativa process.Шаблон:Citation needed

Intermediate halides

A surprising number of intermediate chlorides and bromides are known, but only one iodide, and no difluoride. Rather than the apparent oxidation state of +2, these compounds contain indium in the +1 and +3 oxidation states. Thus the diiodide is described as In^IIn^IIIX₄. It was some time later that the existence of compounds containing the anion Шаблон:Chem2 were confirmed which contains an indium-indium bond. Early work on the chlorides and bromides involved investigations of the binary phase diagrams of the trihalides and the related monohalide. Many of the compounds were initially misidentified as many of them are incongruent and decompose before melting. The majority of the previously reported chlorides and bromides have now either had their existence and structures confirmed by X Ray diffraction studies or have been consigned to history. Perhaps the most unexpected case of mistaken identity was the surprising result that a careful reinvestigation of the InCl/InCl₃ binary phase diagram did not find InCl₂.
The reason for this abundance of compounds is that indium forms 4 and 6 coordinate anions containing indium(III) e.g. Шаблон:Chem2, Шаблон:Chem2 as well as the anion Шаблон:Chem2 that surprisingly contains an indium-indium bond.

In₇Cl₉ and In₇Br₉

In₇Cl₉ is yellow solid stable up to 250 °C that is formulated In^I₆(In^IIICl₆)Cl₃

In₇Br₉ has a similar structure to In₇Cl₉ and can be formulated as In^I₆(In^IIIBr₆)Br₃

In₅Br₇

In₅Br₇ is a pale yellow solid. It is formulated In^I₃(In^II₂Br₆)Br. The In^II₂Br₆ anion has an eclipsed ethane like structure with a metal-metal bond length of 270 pm.

In₂Cl₃ and In₂Br₃

In₂Cl₃ is colourless and is formulated In^I₃ In^IIICl₆ In contrast In₂Br₃ contains the In₂Br₆ anion as present in In₅Br₇, and is formulated In^I₂(In^II₂Br₆) with a structure similar to Ga₂Br₃.

In₄Br₇

In₄Br₇ is near colourless with a pale greenish yellow tint. It is light sensitive (like TlCl and TlBr) decaying to InBr₂ and In metal. It is a mixed salt containing the Шаблон:Chem2 and Шаблон:Chem2 anions balanced by In⁺ cations. It is formulated In^I₅(In^IIIBr₄)₂(In^IIIBr₆) The reasons for the distorted lattice have been ascribed to an antibonding combination between doubly filled, non-directional indium 5s orbitals and neighboring bromine 4p hybrid orbitals.

In₅Cl₉

In₅Cl₉ is formulated as In^I₃In^III₂Cl₉. The Шаблон:Chem2 anion has two 6 coordinate indium atoms with 3 bridging chlorine atoms, face sharing bioctahedra, with a similar structure to Шаблон:Chem2 and Шаблон:Chem2.

InBr₂

InBr₂ is a greenish white crystalline solid, which is formulated In^IIn^III Br₄. It has the same structure as GaCl₂. InBr₂ is soluble in aromatic solvents and some compounds containing η⁶-arene In(I) complexes have been identified. (See hapticity for an explanation of the bonding in such arene-metal ion complexes). With some ligands InBr₂ forms neutral complexes containing an indium-indium bond.

InI₂

InI₂ is a yellow solid that is formulated In^IIn^IIII₄.

Monohalides

The solid monohalides InCl, InBr and InI are all unstable with respect to water, decomposing to the metal and indium(III) species. They fall between gallium(I) compounds, which are more reactive and thallium(I) that are stable with respect to water. InI is the most stable. Up until relatively recently the monohalides have been scientific curiosities, however with the discovery that they can be used to prepare indium cluster and chain compounds they are now attracting much more interest.

InF

InF only known as an unstable gaseous compound.

InCl

Шаблон:Main The room temperature form of InCl is yellow, with a cubic distorted NaCl structure. The red high temperature (>390 K) form has the <chem>\beta-TlI</chem> structure.

InBr

InBr is a red crystalline solid, mp 285 °C. It has the same structure as <chem>\beta-TlI</chem>, with an orthorhombic distorted rock salt structure. It can be prepared from indium metal and InBr₃.

InI

InI is a deep red purple crystalline solid. It has the same structure as <chem>\beta-TlI</chem>. It can be made by direct combination of its constituent elements at high temperature. Alternatively it can be prepared from InI₃ and indium metal in refluxing xylenes. It is the most stable of the solid monohalides and is soluble in some organic solvents. Solutions of InI in a pyridine/m-xylene mixture are stable below 243 K.

Anionic halide complexes of In(III)

The trihalides are Lewis Acids and form addition compounds with ligands. For InF₃ there are few examples known however for the other halides addition compounds with tetrahedral, trigonal bipyramidal and octahedral coordination geometries are known. With halide ions there are examples of all of these geometries along with some anions with octahedrally coordinated indium and with bridging halogen atoms, Шаблон:Chem2 with three bridging halogen atoms and Шаблон:Chem2 with just one. Additionally there are examples of indium with square planar geometry in the InX₅²⁻ ion. The square planar geometry of Шаблон:Chem2 was the first found for a main group element.

Шаблон:Chem2 and Шаблон:Chem2

Salts of Шаблон:Chem2, Шаблон:Chem2 and Шаблон:Chem2 are known. The salt LiInF₄ has been prepared, however it has an unusual layer structure with octahedrally coordinated indium center. Salts of InF₆³⁻, Шаблон:Chem2 and Шаблон:Chem2 have all been made.

Шаблон:Chem2 and Шаблон:Chem2

The Шаблон:Chem2 ion has been found to be square pyramidal in the salt (NEt4)₂InCl₅, with the same structure as (NEt₄)₂ TlCl₅, but is trigonal bipyramidal in tetraphenylphosphonium pentachloroindate acetonitrile solvate.

The Шаблон:Chem2 ion has similarly been found square pyramidal, albeit distorted, in the Bis(4-chloropyridinium) salt and trigonal bipyramidal in Bi₃₇InBr₄₈.

Шаблон:Chem2

The Шаблон:Chem2 ions contain a single bridging halogen atom. Whether the bridge is bent or linear cannot be determined from the spectra. The chloride and bromide have been detected using electrospray mass spectrometry. The Шаблон:Chem2 ion has been prepared in the salt CsIn₂I₇.

Шаблон:Chem2

The caesium salts of Шаблон:Chem2 and Шаблон:Chem2 both contain binuclear anions with octahedrally coordinated Indium atoms.

Anionic halide complexes of In(I) and In(II)

Шаблон:Chem2 and Шаблон:Chem2

In^IX₂⁻ is produced when the In₂X₆²⁻ ion disproportionates. Salts containing the Шаблон:Chem2 ions have been made and their vibrational spectra interpreted as showing that they have C_3v symmetry, trigonal pyramidal geometry, with structures similar to the isoelectronic Шаблон:Chem2 ions.

Шаблон:Chem2, Шаблон:Chem2 and Шаблон:Chem2

Salts of the chloride, bromide and iodide ions Шаблон:Chem2 have been prepared. In non-aqueous solvents this ion disproportionates to give Шаблон:Chem2 and Шаблон:Chem2.

Neutral Indium(II) halide adducts

Following the discovery of the In₂Br₆²⁻ a number of related neutral compounds containing the In^II₂X₄ kernel have been formed from the reaction of indium dihalides with neutral ligands. Some chemists refer to these adducts, when used as the starting point for the synthesis of cluster compounds as ‘In₂X₄’ e.g. the TMEDA adduct.

General sources

• WebElements Periodic Table » Indium » compounds information
• Шаблон:Greenwood&Earnshaw
• Шаблон:Cotton&Wilkinson6th