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

formula	system	space group	unit cell	volume	density	comment	ref
LiTl	cubic	Pmm	a=3.43			melts at 508 °C	^[10]
Li2Tl	orthorhombic	Cmcm	a=4.741 b=10.023 c=4.786			decomposes at 381 °C
Li5Tl2		Rm	a=4.716 c=20.399			melts at 448 °C
Li3Tl	cubic	Fm3m	a=6.67			melts at 447 °C
Li22Tl5 (Li4Tl)	cubic	F3m	a=20.003
NaTl	cubic	Fdm				3D diamond structure mesh for Tl; melts at 305 °C
NaTl	tetragonal	I41/amd	a=5.2341 c=7.5290 Z=4	206.26		grey;
Na2Tl	orthorhombic	C2221	a=13.9350 b=8.8797 c=11.6927			[Tl<sub>4</sub>]^8– tetrahedra; melts at 154 °C
NaTl2						decomposes at 154 °C
Na6Tl	cubic	F3m	a=24.154			melts at 77.4
KTl	orthorhombic	Cmca	a=15.239 b=15.069 c=8.137			[Tl<sub>6</sub>]^6– Compressed octahedra; melts incongruently at 268 °C
K5Tl8						melts at 273 °C
K10Tl7	monoclinic	P21/c	a = 10.132 b = 22.323 c = 13.376 β = 93.14° Z=4
K10Tl6O2						[Tl<sub>6</sub>]^6–
K8Tl11	rhombohedral	Rc	a=9.991 c=5.084			[Tl<sub>11</sub>]^7– pentacapped trigonal prism; melts at 320 °C
K49Tl108		Pm3	a = 17.28.7 Z=1				^[11]
K5Tl17	orthorhombic	Cccm
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	^[12]
K10Tl6O2	orthorhombic	Cmcm	a=8.3755 b=32.102 c=8.8634 Z=4	2383.1	4.597	dark grey
Na7KTl4	orthorhombic	Pbam	a=16.2860 c=11.2771 Z=8	2991.1	4.519	[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>]	monoclinic	P21/c	a=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>]
K8ZnTl10						band gap 0.17 eV
K8GaTl10	tetragonal	P4/nnc	a=10.1858 c=13.6371 Z=2	1414.9	5.695
K49Ga2Tl108
Rb8Tl11						[Tl<sub>11</sub>]^7– pentacapped trigonal prism
Rb15Tl27		P2m					^[15]
Rb17Tl41	hexagonal	Fdm	a = 10.3248 c = 17.558
Rb10Tl6O2	orthorhombic	Cmcm	a=8.7176 b=33.2934 = 9.1242	2648.19	5.300	dark grey; [Tl<sub>6</sub>]^6–
Na7RbTl4	orthorhombic	Pbam	a=16.3584 b=16.3581 c=11.3345 Z=8	3033.0	4.660	@123K [Tl<sub>4</sub>]^8− tetrahedra	^[16]
K4Rb4Tl11Cl0.1	rhombohedral	Rc	a=10.0948 c=51.027 Z=6	4503.3	6.087		^[17]
Rb8GaTl10	tetragonal	P4/nnc	a=10.4714 c=14.0007 Z=2	1535.2	6.051
Rb49Ga2Tl108
Sr3Tl5	orthorhombic	Cmcm	a = 10.604 b = 8.675 c = 10.985 Z = 4	1010.5	8.445	silvery, brittle; [Tl<sub>5</sub>]^6– square pyramidal clusters
YMgTl	hexagonal	P62m	a=7.505 c=4.5985 Z=3		7.05	metallic; black powder	^[18]
Pd3Tl	tetragonal	I4/mmm	a=4.10659 c=15.3028 Z = 4	258.07		Palladothallite	^[19]
SrPdTl2	orthorhombic	Cmcm	a = 4.486 b = 10.991 c = 8.154 Z = 4				^[20]
Na13(Cd~0.70Tl~0.30)27	cubic	Im	a ≃ 15.92 Z = 4			Tl from 0.24 to 0.33	^[21]
K14Cd9Tl21	hexagonal	P2m	a = 9.884 c =17.173 Z = 2				^[22]
Na9K16Tl18Cd3	hexagonal	P63/mmc	a = 11.136 c = 29.352 Z=2				^[23]
Rb5Cd2Tl11	orthorhombic	Amm2	a = 5.5999 b = 17.603 c = 12.896 Z = 2				^[24]
Na12K18In53Tl7		R3m	a=16.846 c=43.339 Z=4				^[25]
Na6TlSb4	monoclinic	C2/c	15.154 b = 10.401 c = 17.413 β = 113.57° Z = 8			metallic	^[26]
K6Tl2Sb3	monoclinic	C2/c	a = 9.951 b = 17.137 c = 19.640 β = 104.26° Z = 8				^[27]
CsTl	orthorhombic	Fddd				[Tl<sub>6</sub>]^6–
Cs3.45K3.55Tl7	tetragonal	I41/a	a = 13.6177 c = 25.5573 Z = 8	4739.3	5.681	[Tl<sub>7</sub>]^7−
Cs7.29K5.71Tl13	monoclinic	C2/c	a = 30.7792 b = 11.000 c = 14.0291 β = 112.676° Z = 4	4382.7	5.835	[Tl<sub>7</sub>]^7− and [Tl<sub>6</sub>]^6–
K3.826Cs4.174Tl11
Cs8Tl11						[Tl<sub>11</sub>]^7– pentacapped trigonal prism
Cs15Tl27	hexagonal	P2m
Cs4Tl2O	trigonal	Rm	a = 11.986 c = 20.370 Z = 9	2534.3	5.640	silvery black; stable to 523 °C; decomposes in air	^[28]
Cs18Tl8O6
Cs10Tl6SiO4	monoclinic	P21/c	a=18.9121 b=11.4386 c=14.8081 β=90.029°			[Tl<sub>6</sub>]^6–
Cs10Tl6GeO4	monoclinic	P21/c	a=19.034 b=11.4883 c=14.8633 β=90.033°			[Tl<sub>6</sub>]^6–
Cs10Tl6SnO3	orthorhombic	Pnma	a=14.8908Å b=19.052 c=11.5855			[Tl<sub>6</sub>]^6–
Rb14CsTl27	hexagonal
Cs8GaTl10	tetragonal	P4/nnc	a=10.777 c=14.354 Z=2	1667.3	6.328
Cs5Cd2Tl11	orthorhombic	Amm2	a = 5.6107 b = 18.090 c = 13.203 Z = 2
Cs8Tl11Pd0.84	rhombohedral	Rc	a = 10.6l0 c = 54.683 Z = 6				^[29]
Cs8Tl11Cl0.8	rhombohedral	Rc	a=10.4691 c=53.297 Z = 6	5058.8	6.578
Cs8Tl11Br0.9	rhombohedral	Rc	a=10.5608 c=53.401 Z = 6	5157.9	6.539
Cs5Rb3Tl11Cl0.5	rhombohedral	Rc	a=10.3791 c=52.437 Z = 6	4892.0	6.502
Cs5.7K2.3Tl11Cl0.6	rhombohedral	Rc	a=10.3291 c=51.909 Z = 6	4796.3	6.469
BaTl2	hexagonal	P63/mmc					^[30]
BaTl4	monoclinic	C2/m	a = 12.408 b = 5.351 c = 10.383 β = 116.00° Z = 4	519.6		silvery	^[31]
LaMgTl	hexagonal	P62m	a=7.813 c=4.7784 Z=3		7.25	metallic; black powder
CeMgTl	hexagonal	P62m	a=7.741 c=4.7375 Z=3		7.47	metallic; black powder
PrMgTl	hexagonal	P62m	a=7.702 c=4.7150 Z=3	242.9	7.60	metallic; black powder
NdMgTl	hexagonal	P62m	a=7.666 c=4.6945 Z=3	242.9	7.74	metallic; black powder
SmMgTl	hexagonal	P62m	a=7.603 c=4.6593 Z=3		8.10	metallic; black powder
EuTl2							^[32]
EuPdTl2	orthorhombic	Cmcm	a=4.466 b=10.767 c=8.120 Z=4	3905	11.35	silvery metallic
GdMgTl	hexagonal	P62m	a=7.556 c=4.6312 Z=3	229.9	7.74	metallic; black powder
TbMgTl	hexagonal	P62m	a=7.518 c=4.6088 Z=3	226.7	8.52	metallic; black powder
DyMgTl	hexagonal	P62m	a=7.495 c=4.5932 Z=3	224.1	8.69	metallic; black powder
HoMgTl	hexagonal	P62m	a=7.471 c=4.5835 Z=3			metallic; black powder
ErMgTl	hexagonal	P62m	a=7.449 c=4.5715 Z=3			metallic; black powder
TmMgTl	hexagonal	P62m	a=7.432 c=4.5541 Z=3			metallic; black powder
LuMgTl	hexagonal	P62m	a=7.402 c=4.5400 Z=3			metallic; black powder
K5TaAs4Tl2	orthorhombic	Pnma					^[33]
Rb5TaAs4Tl2	orthorhombic	Pnma	a = 19.196 b = 11.104 c = 7.894 Z = 4			spiro at Ta
SrPtTl2	orthorhombic	Cmcm	a = 4.491 b = 10.990 c = 8.140 Z = 4
Na12K38Tl48Au2						Tl7 and Tl9 cluster + auride
K3Au5Tl	orthorhombic	Imma	a = 5.595 b =19.706 c =8.430 Z = 4				^[34]
Rb2Au3Tl	orthorhombic	Pmma	a = 5.660 b = 6.741 c = 9.045 Z = 4
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
BaHg0.80Tl3.20	monoclinic	C2/m	a=12.230 b=5.234 c=10.379 β = 115.272	600.3	10.523	silvery

Notes and References

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