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Thallide

From Wikipedia, the free encyclopedia
Class of chemical compounds
Not to be confused withThalidomide.
Example thallide monoclinic Cs7.29K5.71Tl13 containing [Tl6]6− and [Tl7]7− clusters

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

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

Production

[edit]

Thallide compounds can be produced by melting metals together in atantalumcrucible under an inertargon atmosphere.[3] However ifarsenic is included in the mix, it can react with the crucible wall.[9]

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

Properties

[edit]

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

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

Reactions

[edit]

Inliquid ammonia, oxidation occurs yieldingmetal amides, and thallium metal.[2]

Thallides react with water and air.[2]

List

[edit]
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– Compressedoctahedra; melts incongruently at 268 °C[2][12]
K5Tl8melts at 273 °C[12]
K10Tl7monoclinicP21/ca = 10.132b = 22.323c = 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 = 16.625b = 23.594c = 15.369Z = 860288.173@22 °C; metallic; ρ270 = 22.6 μΩ·cm, α = 0.0023 K−1[14]
K10Tl6O2orthorhombicCmcma=8.3755b=32.102c=8.8634 Z=42383.14.597dark grey[7]
Na7KTl4orthorhombicPbama=16.2860c=11.2771Z=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=17.120b=50.71c=16.785β=116.90°[16]
[Et4N]4[Tl4Fe8(CO)30][16]
[Et4N]6[Tl6Fe10(CO)36][16]
K8ZnTl10band gap 0.17 eV[3]
K8GaTl10tetragonalP4/nnca=10.1858c=13.6371Z=21414.95.695[3]
K49Ga2Tl108[3]
Rb8Tl11[Tl11]7– pentacapped trigonal prism[2]
Rb15Tl27P62m[17]
Rb17Tl41hexagonalFd3ma = 10.3248c = 17.558[5]
Rb10Tl6O2orthorhombicCmcma=8.7176b=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=10.0948c=51.027 Z=64503.36.087[6]
Rb8GaTl10tetragonalP4/nnca=10.4714c=14.0007Z=21535.26.051[17]
Rb49Ga2Tl108[3]
Sr3Tl5orthorhombicCmcma = 10.604b = 8.675c = 10.985Z = 41010.58.445silvery, brittle; [Tl5]6– square pyramidal clusters[4]
YMgTlhexagonalP62ma=7.505 c=4.5985 Z=37.05metallic; black powder[19]
Pd3TltetragonalI4/mmma=4.10659c=15.3028Z = 4258.07Palladothallite[20]
SrPdTl2orthorhombicCmcma = 4.486b = 10.991c = 8.154Z = 4[21]
Na13(Cd~0.70Tl~0.30)27cubicIm3a ≃ 15.92Z = 4Tl from 0.24 to 0.33[22]
K14Cd9Tl21hexagonalP2ma = 9.884c =17.173Z = 2[23]
Na9K16Tl18Cd3hexagonalP63/mmca = 11.136c = 29.352 Z=2[24]
Rb5Cd2Tl11orthorhombicAmm2a = 5.5999b = 17.603c = 12.896Z = 2[25]
Na12K18In53Tl7R3ma=16.846c=43.339 Z=4[26]
Na6TlSb4monoclinicC2/c15.154b = 10.401c = 17.413 β = 113.57°Z = 8metallic[27]
K6Tl2Sb3monoclinicC2/ca = 9.951b = 17.137c = 19.640 β = 104.26°Z = 8[27][28]
CsTlorthorhombicFddd[Tl6]6–[2]
Cs3.45K3.55Tl7tetragonalI41/aa = 13.6177c = 25.5573Z = 84739.35.681[Tl7]7−[2]
Cs7.29K5.71Tl13monoclinicC2/ca = 30.7792b = 11.000c = 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 = 11.986c = 20.370Z = 92534.35.640silvery black; stable to 523 °C; decomposes in air[29]
Cs18Tl8O6[29]
Cs10Tl6SiO4monoclinicP21/ca=18.9121b=11.4386c=14.8081β=90.029°[Tl6]6–[2][8]
Cs10Tl6GeO4monoclinicP21/ca=19.034b=11.4883c=14.8633β=90.033°[Tl6]6–[2][8]
Cs10Tl6SnO3orthorhombicPnmaa=14.8908Åb=19.052c=11.5855[Tl6]6–[2][8]
Rb14CsTl27hexagonal[17]
Cs8GaTl10tetragonalP4/nnca=10.777c=14.354Z=21667.36.328[3]
Cs5Cd2Tl11orthorhombicAmm2a = 5.6107b = 18.090c = 13.203Z = 2[25]
Cs8Tl11Pd0.84rhombohedralR3ca = 10.6l0c = 54.683Z = 6[30]
Cs8Tl11Cl0.8rhombohedralR3ca=10.4691c=53.297Z = 65058.86.578[6]
Cs8Tl11Br0.9rhombohedralR3ca=10.5608c=53.401Z = 65157.96.539[6]
Cs5Rb3Tl11Cl0.5rhombohedralR3ca=10.3791c=52.437Z = 64892.06.502[6]
Cs5.7K2.3Tl11Cl0.6rhombohedralR3ca=10.3291c=51.909Z = 64796.36.469[6]
BaTl2hexagonalP63/mmc[31]
BaTl4monoclinicC2/ma = 12.408b = 5.351c = 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 = 19.196b = 11.104c = 7.894Z = 4spiro at Ta[34]
SrPtTl2orthorhombicCmcma = 4.491b = 10.990c = 8.140Z = 4[21]
Na12K38Tl48Au2Tl7 and Tl9 cluster +auride[2]
K3Au5TlorthorhombicImmaa = 5.595b =19.706c =8.430Z = 4[9]
Rb2Au3TlorthorhombicPmmaa = 5.660b = 6.741c = 9.045Z = 4[9]
BaAuTl3tetragonalI4/mmma = 4.8604c = 12.180Z = 2[35]
Ba2AuTl7orthorhombicPmmaa=21.919b=5.193c=10.447[36]
BaAu0.40Tl1.60orthorhombicImmaa = 5.140b = 8.317c = 8.809Z = 4[31]
BaHg0.80Tl3.20monoclinicC2/ma=12.230 b=5.234 c=10.379 β = 115.272600.310.523silvery[32]

References

[edit]
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Neg. ox. states
Thallium(I)
Organothallium(I)
Thallium(III)
Group 1
Group 13
Group 14
Group 15 (Pnictides)
Group 16 (Chalcogenides)
Group 17 (Halides)
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