Thallide
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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- v
- t
- e
- Thallides
- TlN3
- TlOH
- TlI
- TlBr
- Tl2CO3
- TlCl
- TlF
- TlPF6
- TlNO3
- Tl2O
- Tl2SO4
- Tl2S
- Tl2Te
- TlI3
- TBCCO
Organothallium(I) |
---|
- TlH3
- Tl(OH)3
- Tl2O3
- Tl(NO3)3
- Tl(CH3COO)3
- TlF3
- Tl(CF3COO)3