Thallide

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Example thallide monoclinic Cs7.29K5.71Tl13 containing [Tl6] and [Tl7] clusters Cs7.29K5.71Tl13structure.png
Example thallide monoclinic Cs7.29K5.71Tl13 containing [Tl6] and [Tl7] clusters

Thallides are compounds containing anions composed of thallium. There are several thallium atoms in a cluster, and it does not occur as a single Tl− in thallides. [1] [2] They are a subclass of trielides, [2] which also includes gallides and indides. [3] A more general classification is polar intermetallics, as clusters contain delocalized multicentre bonds. [4] Thallides were discovered by Eduard Zintl in 1932. [5]

Contents

Mixed anion compounds with thallides include halides (bromides and chlorides), [6] oxides, [7] and tetrelates (silicate, germanate). [8]

Production

Thallide compounds can be produced by melting metals together in a tantalum crucible under an inert argon atmosphere. [3] However if arsenic is included in the mix, it can react with the crucible wall. [9]

A low temperature production route, is to dissolve an alkali metal in liquid ammonia, and use that to reduce a thallium salt, like thallium iodide. [10]

Properties

Thallide compounds are dense, dense to X-rays and usually metallic grey or black in appearance.

Thallide clusters mostly do not follow Wade-Mingos rules or the Zintl–Klemm concept, as they have too small a negative charge. They can be called "hypoelectronic". [11]

Reactions

In liquid ammonia, oxidation occurs yielding metal amides, and thallium metal. [2]

Thallides react with water and air. [2]

List

formulasystemspace groupunit cellvolumedensitycommentref
LiTlcubicPm3ma=3.43melts at 508 °C [12]
Li2TlorthorhombicCmcma=4.741 b=10.023 c=4.786decomposes at 381 °C [5] [12]
Li5Tl2R3ma=4.716 c=20.399melts at 448 °C [5] [12]
Li3TlcubicFm3ma=6.67melts at 447 °C [5] [12]
Li22Tl5 (Li4Tl)cubicF43ma=20.003 [5] [12]
NaTlcubicFd3m3D diamond structure mesh for Tl; melts at 305 °C [2] [10] [12]
NaTltetragonalI41/amda=5.2341 c=7.5290 Z=4206.26grey; [10] [12]
Na2TlorthorhombicC2221a=13.9350 b=8.8797 c=11.6927[Tl4]8– tetrahedra; melts at 154 °C [2] [12]
NaTl2decomposes at 154 °C [12]
Na6TlcubicF43ma=24.154melts at 77.4 [12]
KTlorthorhombicCmcaa=15.239 b=15.069 c=8.137[Tl6]6– Compressed octahedra; melts incongruently at 268 °C [2] [12]
K5Tl8melts at 273 °C [12]
K10Tl7monoclinicP21/ca = 10.132 b = 22.323 c = 13.376 β = 93.14° Z=4[Tl7]7– pentagonal bipyramid [2]
K10Tl6O2[Tl6]6– [2]
K8Tl11rhombohedralR3ca=9.991 c=5.084[Tl11]7– pentacapped trigonal prism; melts at 320 °C [2] [12]
K49Tl108Pm3a = 17.28.7 Z=1 [13]
K5Tl17orthorhombicCccm [5]
K6Tl17orthorhombicCccma = 16.625 b = 23.594 c = 15.369 Z = 860288.173@22 °C; metallic; ρ270 = 22.6 μΩ·cm, α = 0.0023 K−1 [14]
K10Tl6O2orthorhombicCmcma=8.3755 b=32.102 c=8.8634 Z=42383.14.597dark grey [7]
Na7KTl4orthorhombicPbama=16.2860 c=11.2771 Z=82991.14.519[Tr4]8− [15]
Na9K16Tl~25 [2]
[Et4N]2[{Tl(Fe(CO)4)2}2] [16]
[(PPh2)2N]2[Tl2Fe6(CO)24]monoclinicP21/ca=17.120 b=50.71 c=16.785 β=116.90° [16]
[Et4N]4[Tl4Fe8(CO)30] [16]
[Et4N]6[Tl6Fe10(CO)36] [16]
K8ZnTl10band gap 0.17 eV [3]
K8GaTl10tetragonalP4/nnca=10.1858 c=13.6371 Z=21414.95.695 [3]
K49Ga2Tl108 [3]
Rb8Tl11[Tl11]7– pentacapped trigonal prism [2]
Rb15Tl27P62m [17]
Rb17Tl41hexagonalFd3ma = 10.3248 c = 17.558 [5]
Rb10Tl6O2orthorhombicCmcma=8.7176 b=33.2934 = 9.12422648.195.300dark grey; [Tl6]6– [2] [7]
Na7RbTl4orthorhombicPbama=16.3584 b=16.3581 c=11.3345 Z=83033.04.660@123K [Tl4]8− tetrahedra [18]
K4Rb4Tl11Cl0.1rhombohedralR3ca=10.0948 c=51.027 Z=64503.36.087 [6]
Rb8GaTl10tetragonalP4/nnca=10.4714 c=14.0007 Z=21535.26.051 [17]
Rb49Ga2Tl108 [3]
Sr3Tl5orthorhombicCmcma = 10.604 b = 8.675 c = 10.985 Z = 41010.58.445silvery, brittle; [Tl5]6– square pyramidal clusters [4]
YMgTlhexagonalP62ma=7.505 c=4.5985 Z=37.05metallic; black powder [19]
Pd3TltetragonalI4/mmma=4.10659 c=15.3028 Z = 4258.07Palladothallite [20]
SrPdTl2orthorhombicCmcma = 4.486 b = 10.991 c = 8.154 Z = 4 [21]
Na13(Cd~0.70Tl~0.30)27cubicIm3a ≃ 15.92 Z = 4Tl from 0.24 to 0.33 [22]
K14Cd9Tl21hexagonalP2ma = 9.884 c =17.173 Z = 2 [23]
Na9K16Tl18Cd3hexagonalP63/mmca = 11.136 c = 29.352 Z=2 [24]
Rb5Cd2Tl11orthorhombicAmm2a = 5.5999 b = 17.603 c = 12.896 Z = 2 [25]
Na12K18In53Tl7R3ma=16.846 c=43.339 Z=4 [26]
Na6TlSb4monoclinicC2/c15.154 b = 10.401 c = 17.413 β = 113.57° Z = 8metallic [27]
K6Tl2Sb3monoclinicC2/ca = 9.951 b = 17.137 c = 19.640 β = 104.26° Z = 8 [27] [28]
CsTlorthorhombicFddd[Tl6]6– [2]
Cs3.45K3.55Tl7tetragonalI41/aa = 13.6177 c = 25.5573 Z = 84739.35.681[Tl7]7− [2]
Cs7.29K5.71Tl13monoclinicC2/ca = 30.7792 b = 11.000 c = 14.0291 β = 112.676° Z = 44382.75.835[Tl7]7− and [Tl6]6– [2]
K3.826Cs4.174Tl11 [2]
Cs8Tl11[Tl11]7– pentacapped trigonal prism [2]
Cs15Tl27hexagonalP62m [5] [17]
Cs4Tl2OtrigonalR3ma = 11.986 c = 20.370 Z = 92534.35.640silvery black; stable to 523 °C; decomposes in air [29]
Cs18Tl8O6 [29]
Cs10Tl6SiO4monoclinicP21/ca=18.9121 b=11.4386 c=14.8081 β=90.029°[Tl6]6– [2] [8]
Cs10Tl6GeO4monoclinicP21/ca=19.034 b=11.4883 c=14.8633 β=90.033°[Tl6]6– [2] [8]
Cs10Tl6SnO3orthorhombicPnmaa=14.8908Å b=19.052 c=11.5855[Tl6]6– [2] [8]
Rb14CsTl27hexagonal [17]
Cs8GaTl10tetragonalP4/nnca=10.777 c=14.354 Z=21667.36.328 [3]
Cs5Cd2Tl11orthorhombicAmm2a = 5.6107 b = 18.090 c = 13.203 Z = 2 [25]
Cs8Tl11Pd0.84rhombohedralR3ca = 10.6l0 c = 54.683 Z = 6 [30]
Cs8Tl11Cl0.8rhombohedralR3ca=10.4691 c=53.297 Z = 65058.86.578 [6]
Cs8Tl11Br0.9rhombohedralR3ca=10.5608 c=53.401 Z = 65157.96.539 [6]
Cs5Rb3Tl11Cl0.5rhombohedralR3ca=10.3791 c=52.437 Z = 64892.06.502 [6]
Cs5.7K2.3Tl11Cl0.6rhombohedralR3ca=10.3291 c=51.909 Z = 64796.36.469 [6]
BaTl2hexagonalP63/mmc [31]
BaTl4monoclinicC2/ma = 12.408 b = 5.351 c = 10.383 β = 116.00° Z = 4519.6silvery [32]
LaMgTlhexagonalP62ma=7.813 c=4.7784 Z=37.25metallic; black powder [19]
CeMgTlhexagonalP62ma=7.741 c=4.7375 Z=37.47metallic; black powder [19]
PrMgTlhexagonalP62ma=7.702 c=4.7150 Z=3242.97.60metallic; black powder [19]
NdMgTlhexagonalP62ma=7.666 c=4.6945 Z=3242.97.74metallic; black powder [19]
SmMgTlhexagonalP62ma=7.603 c=4.6593 Z=38.10metallic; black powder [19]
EuTl2 [33]
EuPdTl2orthorhombicCmcma=4.466 b=10.767 c=8.120 Z=4390511.35silvery metallic [33]
GdMgTlhexagonalP62ma=7.556 c=4.6312 Z=3229.97.74metallic; black powder [19]
TbMgTlhexagonalP62ma=7.518 c=4.6088 Z=3226.78.52metallic; black powder [19]
DyMgTlhexagonalP62ma=7.495 c=4.5932 Z=3224.18.69metallic; black powder [19]
HoMgTlhexagonalP62ma=7.471 c=4.5835 Z=3metallic; black powder [19]
ErMgTlhexagonalP62ma=7.449 c=4.5715 Z=3metallic; black powder [19]
TmMgTlhexagonalP62ma=7.432 c=4.5541 Z=3metallic; black powder [19]
LuMgTlhexagonalP62ma=7.402 c=4.5400 Z=3metallic; black powder [19]
K5TaAs4Tl2orthorhombicPnma [34]
Rb5TaAs4Tl2orthorhombicPnmaa = 19.196 b = 11.104 c = 7.894 Z = 4spiro at Ta [34]
SrPtTl2orthorhombicCmcma = 4.491 b = 10.990 c = 8.140 Z = 4 [21]
Na12K38Tl48Au2Tl7 and Tl9 cluster + auride [2]
K3Au5TlorthorhombicImmaa = 5.595 b =19.706 c =8.430 Z = 4 [9]
Rb2Au3TlorthorhombicPmmaa = 5.660 b = 6.741 c = 9.045 Z = 4 [9]
BaAuTl3tetragonalI4/mmma = 4.8604 c = 12.180 Z = 2 [35]
Ba2AuTl7orthorhombicPmmaa=21.919 b=5.193 c=10.447 [36]
BaAu0.40Tl1.60orthorhombicImmaa = 5.140 b = 8.317 c = 8.809 Z = 4 [31]
BaHg0.80Tl3.20monoclinicC2/ma=12.230 b=5.234 c=10.379 β = 115.272600.310.523silvery [32]

Related Research Articles

In chemistry, a Zintl phase is a product of a reaction between a group 1 or group 2 and main group metal or metalloid. It is characterized by intermediate metallic/ionic bonding. Zintl phases are a subgroup of brittle, high-melting intermetallic compounds that are diamagnetic or exhibit temperature-independent paramagnetism and are poor conductors or semiconductors.

A stannide can refer to an intermetallic compound containing tin combined with one or more other metals; an anion consisting solely of tin atoms or a compound containing such an anion, or, in the field of organometallic chemistry an ionic compound containing an organotin anion

A selenite fluoride is a chemical compound or salt that contains fluoride and selenite anions. These are mixed anion compounds. Some have third anions, including nitrate, molybdate, oxalate, selenate, silicate and tellurate.

The borosulfates are heteropoly anion compounds which have sulfate groups attached to boron atoms. Other possible terms are sulfatoborates or boron-sulfur oxides. The ratio of sulfate to borate reflects the degree of condensation. With [B(SO4)4]5- there is no condensation, each ion stands alone. In [B(SO4)3]3- the anions are linked into a chain, a chain of loops, or as [B2(SO4)6]6− in a cycle. Finally in [B(SO4)2]− the sulfate and borate tetrahedra are all linked into a two or three-dimensional network. These arrangements of oxygen around boron and sulfur can have forms resembling silicates. The first borosulfate to be discovered was K5[B(SO4)4] in 2012 by the research group of Henning Höppe, although the compound class as such had been postulated already in 1962 by G. Schott and H. U. Kibbel. Over 80 unique compounds are known as of 2024.

The borophosphates are mixed anion compounds containing borate and phosphate anions, which may be joined together by a common oxygen atom. Compounds that contain water or hydroxy groups can also be included in the class of compounds.

Selenogallates are chemical compounds which contain anionic units of selenium connected to gallium. They can be considered as gallates where selenium substitutes for oxygen. Similar compounds include the thiogallates and selenostannates. They are in the category of chalcogenotrielates or more broadly chalcogenometallates.

Sulfidostannates, or thiostannates are chemical compounds containing anions composed of tin linked with sulfur. They can be considered as stannates with sulfur substituting for oxygen. Related compounds include the thiosilicates, and thiogermanates, and by varying the chalcogen: selenostannates, and tellurostannates. Oxothiostannates have oxygen in addition to sulfur. Thiostannates can be classed as chalcogenidometalates, thiometallates, chalcogenidotetrelates, thiotetrelates, and chalcogenidostannates. Tin is almost always in the +4 oxidation state in thiostannates, although a couple of mixed sulfides in the +2 state are known,

<span class="mw-page-title-main">Silanide</span> Anionic molecule derived from silane

A silanide is a chemical compound containing an anionic silicon(IV) centre, the parent ion being SiH−3. The hydrogen atoms can also be substituted to produce more complex derivative anions such as tris(trimethylsilyl)silanide (hypersilyl), tris(tert-butyl)silanide, tris(pentafluoroethyl)silanide, or triphenylsilanide. The simple silanide ion can also be called trihydridosilanide or silyl hydride.

Arsenidosilicates are chemical compounds that contain anions with arsenic bonded to silicon. They are in the category of tetrelarsenides, pnictidosilicates, or tetrelpnictides. They can be classed as Zintl phases or intermetallics. They are analogous to the nitridosilicates, phosphidosilicates, arsenidogermanates, and arsenidostannates. They are distinct from arsenate silicates which have oxygen connected with arsenic and silicon, or arsenatosilicates with arsenate groups sharing oxygen with silicate.

Arsenidostanates are chemical compounds that contain anions with arsenic bonded to tin. They are in the category of tetrelarsenides, pnictidostancates, or tetrelpnictides.

Selenidogermanates are compounds with anions with selenium bound to germanium. They are analogous with germanates, thiogermanates, and telluridogermanates.

Sulfidogermanates or thiogermanates are chemical compounds containing anions with sulfur atoms bound to germanium. They are in the class of chalcogenidotetrelates. Related compounds include thiosilicates, thiostannates, selenidogermanates, telluridogermanates and selenidostannates.

Phosphide iodides or iodide phosphides are compounds containing anions composed of iodide (I−) and phosphide (P3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the phosphide chlorides, arsenide iodides antimonide iodides and phosphide bromides.

Carbide chlorides are mixed anion compounds containing chloride anions and anions consisting entirely of carbon. In these compounds there is no bond between chlorine and carbon. But there is a bond between a metal and carbon. Many of these compounds are cluster compounds, in which metal atoms encase a carbon core, with chlorine atoms surrounding the cluster. The chlorine may be shared between clusters to form polymers or layers. Most carbide chloride compounds contain rare earth elements. Some are known from group 4 elements. The hexatungsten carbon cluster can be oxidised and reduced, and so have different numbers of chlorine atoms included.

Carbide bromides are mixed anion compounds containing bromide and carbide anions. Many carbide bromides are cluster compounds, containing on, two or more carbon atoms in a core, surrounded by a layer of metal atoms, encased in a shell of bromide ions. These ions may be shared between clusters to form chains, double chains or layers.

Carbide iodides are mixed anion compounds containing iodide and carbide anions. Many carbide iodides are cluster compounds, containing one, two or more carbon atoms in a core, surrounded by a layer of metal atoms, and encased in a shell of iodide ions. These ions may be shared between clusters to form chains, double chains or layers.

Iodide hydrides are mixed anion compounds containing hydride and iodide anions. Many iodide hydrides are cluster compounds, containing a hydrogen atom in a core, surrounded by a layer of metal atoms, encased in a shell of iodide.

Selenidostannates are chemical compounds which contain anionic units of selenium connected to tin. They can be considered as stannates where selenium substitutes for oxygen. Similar compounds include the selenogermanates and thiostannates. They are in the category of chalcogenidotetrelates or more broadly chalcogenometallates.

Tellurogermanates or telluridogermanates are compounds with anions with tellurium bound to germanium. They are analogous with germanates, thiogermanates and selenidogermanates.

A selenophosphate is a chemical compound containing phosphate anions substituted with selenium. Over 7000 compounds are known with a bond between selenium and phosphorus. Compared to phosphorus-sulfur compounds selenophosphates are less thermally stable, and more easily destroyed by water. However they are more stable than tellurophosphates which have an even weaker phosphorus-tellurium bond. Selenophosphates have an oxidation number for phosphorus of +5. But in many there are bonds between phosphorus atoms, reducing the oxidation state to +4, Some may be termed selenophosphites.

References

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  24. ↑ Huang, DaPing; Corbett, John D. (1999-01-01). "Na 9 K 16 Tl 18 Cd 3 : A Novel Phase Containing Tl 8 Cd 3 10 - and Tl 5 7 - Clusters 1". Inorganic Chemistry. 38 (2): 316–320. doi:10.1021/ic9807792. ISSN   0020-1669.
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  26. ↑ Flot, David; Tillard-Charbonnel, Monique; Belin, Claude (1998). "Na12K18In53Tl7: a novel mixed In/Tl phase hierarchically related to the C15 Friauf–Laves structure type. Synthesis, crystal and electronic structure". New Journal of Chemistry. 22 (6): 591–598. doi:10.1039/a708761f.
  27. 1 2 Li, Bin; Chi, Lisheng; Corbett, John D. (2003-05-01). "Na 6 TlSb 4 : Synthesis, Structure, and Bonding. An Electron-Rich Salt with a Chain Conformation and a Tl−Tl Bond Length Determined by the Cation". Inorganic Chemistry. 42 (9): 3036–3042. doi:10.1021/ic020728b. ISSN   0020-1669. PMID   12716198.
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  33. 1 2 Kraft, Rainer; Rayaprol, Sudhindra; Sebastian, C. Peter; Pöttgen, Rainer (2006-02-01). "Ferromagnetic Ordering in the Thallide EuPdTl 2". Zeitschrift für Naturforschung B. 61 (2): 159–163. doi: 10.1515/znb-2006-0207 . ISSN   1865-7117.
  34. 1 2 Huang, DaPing; Corbett, John D. (1998-08-01). "A 5 TaAs 4 Tl 2 (A = Rb, K). Transition-Metal Zintl Phases with a Novel Complex Ion: Synthesis, Structure, and Bonding". Inorganic Chemistry. 37 (16): 4006–4010. doi:10.1021/ic9802395. ISSN   0020-1669. PMID   11670516.
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