Thallide Explained

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, 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), oxides,[6] and tetrelates (silicate, germanate).[7]

Production

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

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.[8]

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".[9]

Reactions

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

Thallides react with water and air.

List

formulasystemspace groupunit cellvolumedensitycommentref
LiTlcubicPmma=3.43melts at 508 °C[10]
Li2TlorthorhombicCmcma=4.741 b=10.023 c=4.786decomposes at 381 °C
Li5Tl2Rma=4.716 c=20.399melts at 448 °C
Li3TlcubicFm3ma=6.67melts at 447 °C
Li22Tl5 (Li4Tl)cubicF3ma=20.003
NaTlcubicFdm3D diamond structure mesh for Tl; melts at 305 °C
NaTltetragonalI41/amda=5.2341 c=7.5290 Z=4206.26grey;
Na2TlorthorhombicC2221a=13.9350 b=8.8797 c=11.6927[Tl<sub>4</sub>]8– tetrahedra; melts at 154 °C
NaTl2decomposes at 154 °C
Na6TlcubicF3ma=24.154melts at 77.4
KTlorthorhombicCmcaa=15.239 b=15.069 c=8.137[Tl<sub>6</sub>]6– Compressed octahedra; melts incongruently at 268 °C
K5Tl8melts at 273 °C
K10Tl7monoclinicP21/ca = 10.132 b = 22.323 c = 13.376 β = 93.14° Z=4
K10Tl6O2[Tl<sub>6</sub>]6–
K8Tl11rhombohedralRca=9.991 c=5.084[Tl<sub>11</sub>]7– pentacapped trigonal prism; melts at 320 °C
K49Tl108Pm3a = 17.28.7 Z=1[11]
K5Tl17orthorhombicCccm
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[12]
K10Tl6O2orthorhombicCmcma=8.3755 b=32.102 c=8.8634 Z=42383.14.597dark grey
Na7KTl4orthorhombicPbama=16.2860 c=11.2771 Z=82991.14.519[Tr<sub>4</sub>]8−[13]
Na9K16Tl~25
[Et<sub>4</sub>N]2[{Tl(Fe(CO)<sub>4</sub>)<sub>2</sub>}<sub>2</sub>][14]
[(PPh<sub>2</sub>)<sub>2</sub>N]2[Tl<sub>2</sub>Fe<sub>6</sub>(CO)<sub>24</sub>]monoclinicP21/ca=17.120 b=50.71 c=16.785 β=116.90°
[Et<sub>4</sub>N]4[Tl<sub>4</sub>Fe<sub>8</sub>(CO)<sub>30</sub>]
[Et<sub>4</sub>N]6[Tl<sub>6</sub>Fe<sub>10</sub>(CO)<sub>36</sub>]
K8ZnTl10band gap 0.17 eV
K8GaTl10tetragonalP4/nnca=10.1858 c=13.6371 Z=21414.95.695
K49Ga2Tl108
Rb8Tl11[Tl<sub>11</sub>]7– pentacapped trigonal prism
Rb15Tl27P2m[15]
Rb17Tl41hexagonalFdma = 10.3248 c = 17.558
Rb10Tl6O2orthorhombicCmcma=8.7176 b=33.2934 = 9.12422648.195.300dark grey; [Tl<sub>6</sub>]6–
Na7RbTl4orthorhombicPbama=16.3584 b=16.3581 c=11.3345 Z=83033.04.660@123K [Tl<sub>4</sub>]8− tetrahedra[16]
K4Rb4Tl11Cl0.1rhombohedralRca=10.0948 c=51.027 Z=64503.36.087[17]
Rb8GaTl10tetragonalP4/nnca=10.4714 c=14.0007 Z=21535.26.051
Rb49Ga2Tl108
Sr3Tl5orthorhombicCmcma = 10.604 b = 8.675 c = 10.985 Z = 41010.58.445silvery, brittle; [Tl<sub>5</sub>]6– square pyramidal clusters
YMgTlhexagonalP62ma=7.505 c=4.5985 Z=37.05metallic; black powder[18]
Pd3TltetragonalI4/mmma=4.10659 c=15.3028 Z = 4258.07Palladothallite[19]
SrPdTl2orthorhombicCmcma = 4.486 b = 10.991 c = 8.154 Z = 4[20]
Na13(Cd~0.70Tl~0.30)27cubicIma ≃ 15.92 Z = 4Tl from 0.24 to 0.33[21]
K14Cd9Tl21hexagonalP2ma = 9.884 c =17.173 Z = 2[22]
Na9K16Tl18Cd3hexagonalP63/mmca = 11.136 c = 29.352 Z=2[23]
Rb5Cd2Tl11orthorhombicAmm2a = 5.5999 b = 17.603 c = 12.896 Z = 2[24]
Na12K18In53Tl7R3ma=16.846 c=43.339 Z=4[25]
Na6TlSb4monoclinicC2/c15.154 b = 10.401 c = 17.413 β = 113.57° Z = 8metallic[26]
K6Tl2Sb3monoclinicC2/ca = 9.951 b = 17.137 c = 19.640 β = 104.26° Z = 8[27]
CsTlorthorhombicFddd[Tl<sub>6</sub>]6–
Cs3.45K3.55Tl7tetragonalI41/aa = 13.6177 c = 25.5573 Z = 84739.35.681[Tl<sub>7</sub>]7−
Cs7.29K5.71Tl13monoclinicC2/ca = 30.7792 b = 11.000 c = 14.0291 β = 112.676° Z = 44382.75.835[Tl<sub>7</sub>]7− and [Tl<sub>6</sub>]6–
K3.826Cs4.174Tl11
Cs8Tl11[Tl<sub>11</sub>]7– pentacapped trigonal prism
Cs15Tl27hexagonalP2m
Cs4Tl2OtrigonalRma = 11.986 c = 20.370 Z = 92534.35.640silvery black; stable to 523 °C; decomposes in air[28]
Cs18Tl8O6
Cs10Tl6SiO4monoclinicP21/ca=18.9121 b=11.4386 c=14.8081 β=90.029°[Tl<sub>6</sub>]6–
Cs10Tl6GeO4monoclinicP21/ca=19.034 b=11.4883 c=14.8633 β=90.033°[Tl<sub>6</sub>]6–
Cs10Tl6SnO3orthorhombicPnmaa=14.8908Å b=19.052 c=11.5855[Tl<sub>6</sub>]6–
Rb14CsTl27hexagonal
Cs8GaTl10tetragonalP4/nnca=10.777 c=14.354 Z=21667.36.328
Cs5Cd2Tl11orthorhombicAmm2a = 5.6107 b = 18.090 c = 13.203 Z = 2
Cs8Tl11Pd0.84rhombohedralRca = 10.6l0 c = 54.683 Z = 6[29]
Cs8Tl11Cl0.8rhombohedralRca=10.4691 c=53.297 Z = 65058.86.578
Cs8Tl11Br0.9rhombohedralRca=10.5608 c=53.401 Z = 65157.96.539
Cs5Rb3Tl11Cl0.5rhombohedralRca=10.3791 c=52.437 Z = 64892.06.502
Cs5.7K2.3Tl11Cl0.6rhombohedralRca=10.3291 c=51.909 Z = 64796.36.469
BaTl2hexagonalP63/mmc[30]
BaTl4 monoclinicC2/ma = 12.408 b = 5.351 c = 10.383 β = 116.00° Z = 4519.6silvery[31]
LaMgTlhexagonalP62ma=7.813 c=4.7784 Z=37.25metallic; black powder
CeMgTlhexagonalP62ma=7.741 c=4.7375 Z=37.47metallic; black powder
PrMgTlhexagonalP62ma=7.702 c=4.7150 Z=3242.97.60metallic; black powder
NdMgTlhexagonalP62ma=7.666 c=4.6945 Z=3242.97.74metallic; black powder
SmMgTlhexagonalP62ma=7.603 c=4.6593 Z=38.10metallic; black powder
EuTl2[32]
EuPdTl2orthorhombicCmcma=4.466 b=10.767 c=8.120 Z=4390511.35silvery metallic
GdMgTlhexagonalP62ma=7.556 c=4.6312 Z=3229.97.74metallic; black powder
TbMgTlhexagonalP62ma=7.518 c=4.6088 Z=3226.78.52metallic; black powder
DyMgTlhexagonalP62ma=7.495 c=4.5932 Z=3224.18.69metallic; black powder
HoMgTlhexagonalP62ma=7.471 c=4.5835 Z=3metallic; black powder
ErMgTlhexagonalP62ma=7.449 c=4.5715 Z=3metallic; black powder
TmMgTlhexagonalP62ma=7.432 c=4.5541 Z=3metallic; black powder
LuMgTlhexagonalP62ma=7.402 c=4.5400 Z=3metallic; black powder
K5TaAs4Tl2orthorhombicPnma[33]
Rb5TaAs4Tl2orthorhombicPnmaa = 19.196 b = 11.104 c = 7.894 Z = 4spiro at Ta
SrPtTl2orthorhombicCmcma = 4.491 b = 10.990 c = 8.140 Z = 4
Na12K38Tl48Au2Tl7 and Tl9 cluster + auride
K3Au5TlorthorhombicImmaa = 5.595 b =19.706 c =8.430 Z = 4[34]
Rb2Au3TlorthorhombicPmmaa = 5.660 b = 6.741 c = 9.045 Z = 4
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
BaHg0.80Tl3.20monoclinicC2/ma=12.230 b=5.234 c=10.379 β = 115.272600.310.523silvery

Notes and References

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