Thallide

Not to be confused with Thalidomide.

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]

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

formula system space group unit cell volume density comment ref
LiTl cubic Pm3m a=3.43 melts at 508 °C [12]
Li2Tl orthorhombic Cmcm a=4.741 b=10.023 c=4.786 decomposes at 381 °C [5][12]
Li5Tl2 R3m a=4.716 c=20.399 melts at 448 °C [5][12]
Li3Tl cubic Fm3m a=6.67 melts at 447 °C [5][12]
Li22Tl5 (Li4Tl) cubic F43m a=20.003 [5][12]
NaTl cubic Fd3m 3D diamond structure mesh for Tl; melts at 305 °C [2][10][12]
NaTl tetragonal I41/amd a=5.2341 c=7.5290 Z=4 206.26 grey; [10][12]
Na2Tl orthorhombic C2221 a=13.9350 b=8.8797 c=11.6927 [Tl4]8– tetrahedra; melts at 154 °C [2][12]
NaTl2 decomposes at 154 °C [12]
Na6Tl cubic F43m a=24.154 melts at 77.4 [12]
KTl orthorhombic Cmca a=15.239 b=15.069 c=8.137 [Tl6]6– Compressed octahedra; melts incongruently at 268 °C [2][12]
K5Tl8 melts at 273 °C [12]
K10Tl7 monoclinic P21/c a = 10.132 b = 22.323 c = 13.376 β = 93.14° Z=4 [Tl7]7– pentagonal bipyramid [2]
K10Tl6O2 [Tl6]6– [2]
K8Tl11 rhombohedral R3c a=9.991 c=5.084 [Tl11]7– pentacapped trigonal prism; melts at 320 °C [2][12]
K49Tl108 Pm3 a = 17.28.7 Z=1 [13]
K5Tl17 orthorhombic Cccm [5]
K6Tl17 orthorhombic Cccm a = 16.625 b = 23.594 c = 15.369 Z = 8 6028 8.173 @22 °C; metallic; ρ270 = 22.6 μΩ·cm, α = 0.0023 K-1 [14]
K10Tl6O2 orthorhombic Cmcm a=8.3755 b=32.102 c=8.8634 Z=4 2383.1 4.597 dark grey [7]
Na7KTl4 orthorhombic Pbam a=16.2860 c=11.2771 Z=8 2991.1 4.519 [Tr4]8− [15]
Na9K16Tl~25 [2]
[Et4N]2[{Tl(Fe(CO)4)2}2] [16]
[(PPh2)2N]2[Tl2Fe6(CO)24] monoclinic P21/c a=17.120 b=50.71 c=16.785 β=116.90° [16]
[Et4N]4[Tl4Fe8(CO)30] [16]
[Et4N]6[Tl6Fe10(CO)36] [16]
K8ZnTl10 band gap 0.17 eV [3]
K8GaTl10 tetragonal P4/nnc a=10.1858 c=13.6371 Z=2 1414.9 5.695 [3]
K49Ga2Tl108 [3]
Rb8Tl11 [Tl11]7– pentacapped trigonal prism [2]
Rb15Tl27 P62m [17]
Rb17Tl41 hexagonal Fd3m a = 10.3248 c = 17.558 [5]
Rb10Tl6O2 orthorhombic Cmcm a=8.7176 b=33.2934 = 9.1242 2648.19 5.300 dark grey; [Tl6]6– [2][7]
Na7RbTl4 orthorhombic Pbam a=16.3584 b=16.3581 c=11.3345 Z=8 3033.0 4.660 @123K [Tl4]8− tetrahedra [18]
K4Rb4Tl11Cl0.1 rhombohedral R3c a=10.0948 c=51.027 Z=6 4503.3 6.087 [6]
Rb8GaTl10 tetragonal P4/nnc a=10.4714 c=14.0007 Z=2 1535.2 6.051 [17]
Rb49Ga2Tl108 [3]
Sr3Tl5 orthorhombic Cmcm a = 10.604 b = 8.675 c = 10.985 Z = 4 1010.5 8.445 silvery, brittle; [Tl5]6– square pyramidal clusters [4]
YMgTl hexagonal P62m a=7.505 c=4.5985 Z=3 7.05 metallic; black powder [19]
Pd3Tl tetragonal I4/mmm a=4.10659 c=15.3028 Z = 4 258.07 Palladothallite [20]
SrPdTl2 orthorhombic Cmcm a = 4.486 b = 10.991 c = 8.154 Z = 4 [21]
Na13(Cd~0.70Tl~0.30)27 cubic Im3 a ≃ 15.92 Z = 4 Tl from 0.24 to 0.33 [22]
K14Cd9Tl21 hexagonal P2m a = 9.884 c =17.173 Z = 2 [23]
Na9K16Tl18Cd3 hexagonal P63/mmc a = 11.136 c = 29.352 Z=2 [24]
Rb5Cd2Tl11 orthorhombic Amm2 a = 5.5999 b = 17.603 c = 12.896 Z = 2 [25]
Na12K18In53Tl7 R3m a=16.846 c=43.339 Z=4 [26]
Na6TlSb4 monoclinic C2/c 15.154 b = 10.401 c = 17.413 β = 113.57° Z = 8 metallic [27]
K6Tl2Sb3 monoclinic C2/c a = 9.951 b = 17.137 c = 19.640 β = 104.26° Z = 8 [27][28]
CsTl orthorhombic Fddd [Tl6]6– [2]
Cs3.45K3.55Tl7 tetragonal I41/a a = 13.6177 c = 25.5573 Z = 8 4739.3 5.681 [Tl7]7− [2]
Cs7.29K5.71Tl13 monoclinic C2/c a = 30.7792 b = 11.000 c = 14.0291 β = 112.676° Z = 4 4382.7 5.835 [Tl7]7− and [Tl6]6– [2]
K3.826Cs4.174Tl11 [2]
Cs8Tl11 [Tl11]7– pentacapped trigonal prism [2]
Cs15Tl27 hexagonal P62m [5][17]
Cs4Tl2O trigonal R3m a = 11.986 c = 20.370 Z = 9 2534.3 5.640 silvery black; stable to 523 °C; decomposes in air [29]
Cs18Tl8O6 [29]
Cs10Tl6SiO4 monoclinic P21/c a=18.9121 b=11.4386 c=14.8081 β=90.029° [Tl6]6– [2][8]
Cs10Tl6GeO4 monoclinic P21/c a=19.034 b=11.4883 c=14.8633 β=90.033° [Tl6]6– [2][8]
Cs10Tl6SnO3 orthorhombic Pnma a=14.8908Å b=19.052 c=11.5855 [Tl6]6– [2][8]
Rb14CsTl27 hexagonal [17]
Cs8GaTl10 tetragonal P4/nnc a=10.777 c=14.354 Z=2 1667.3 6.328 [3]
Cs5Cd2Tl11 orthorhombic Amm2 a = 5.6107 b = 18.090 c = 13.203 Z = 2 [25]
Cs8Tl11Pd0.84 rhombohedral R3c a = 10.6l0 c = 54.683 Z = 6 [30]
Cs8Tl11Cl0.8 rhombohedral R3c a=10.4691 c=53.297 Z = 6 5058.8 6.578 [6]
Cs8Tl11Br0.9 rhombohedral R3c a=10.5608 c=53.401 Z = 6 5157.9 6.539 [6]
Cs5Rb3Tl11Cl0.5 rhombohedral R3c a=10.3791 c=52.437 Z = 6 4892.0 6.502 [6]
Cs5.7K2.3Tl11Cl0.6 rhombohedral R3c a=10.3291 c=51.909 Z = 6 4796.3 6.469 [6]
BaTl2 hexagonal P63/mmc [31]
BaTl4 monoclinic C2/m a = 12.408 b = 5.351 c = 10.383 β = 116.00° Z = 4 519.6 silvery [32]
LaMgTl hexagonal P62m a=7.813 c=4.7784 Z=3 7.25 metallic; black powder [19]
CeMgTl hexagonal P62m a=7.741 c=4.7375 Z=3 7.47 metallic; black powder [19]
PrMgTl hexagonal P62m a=7.702 c=4.7150 Z=3 242.9 7.60 metallic; black powder [19]
NdMgTl hexagonal P62m a=7.666 c=4.6945 Z=3 242.9 7.74 metallic; black powder [19]
SmMgTl hexagonal P62m a=7.603 c=4.6593 Z=3 8.10 metallic; black powder [19]
EuTl2 [33]
EuPdTl2 orthorhombic Cmcm a=4.466 b=10.767 c=8.120 Z=4 3905 11.35 silvery metallic [33]
GdMgTl hexagonal P62m a=7.556 c=4.6312 Z=3 229.9 7.74 metallic; black powder [19]
TbMgTl hexagonal P62m a=7.518 c=4.6088 Z=3 226.7 8.52 metallic; black powder [19]
DyMgTl hexagonal P62m a=7.495 c=4.5932 Z=3 224.1 8.69 metallic; black powder [19]
HoMgTl hexagonal P62m a=7.471 c=4.5835 Z=3 metallic; black powder [19]
ErMgTl hexagonal P62m a=7.449 c=4.5715 Z=3 metallic; black powder [19]
TmMgTl hexagonal P62m a=7.432 c=4.5541 Z=3 metallic; black powder [19]
LuMgTl hexagonal P62m a=7.402 c=4.5400 Z=3 metallic; black powder [19]
K5TaAs4Tl2 orthorhombic Pnma [34]
Rb5TaAs4Tl2 orthorhombic Pnma a = 19.196 b = 11.104 c = 7.894 Z = 4 spiro at Ta [34]
SrPtTl2 orthorhombic Cmcm a = 4.491 b = 10.990 c = 8.140 Z = 4 [21]
Na12K38Tl48Au2 Tl7 and Tl9 cluster + auride [2]
K3Au5Tl orthorhombic Imma a = 5.595 b =19.706 c =8.430 Z = 4 [9]
Rb2Au3Tl orthorhombic Pmma a = 5.660 b = 6.741 c = 9.045 Z = 4 [9]
BaAuTl3 tetragonal I4/mmm a = 4.8604 c = 12.180 Z = 2 [35]
Ba2AuTl7 orthorhombic Pmma a=21.919 b=5.193 c=10.447 [36]
BaAu0.40Tl1.60 orthorhombic Imma a = 5.140 b = 8.317 c = 8.809 Z = 4 [31]
BaHg0.80Tl3.20 monoclinic C2/m a=12.230 b=5.234 c=10.379 β = 115.272 600.3 10.523 silvery [32]

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