Lutetium compounds

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Lutetium compounds are compounds formed by the lanthanide metal lutetium (Lu). In these compounds, lutetium generally exhibits the +3 oxidation state, such as LuCl3, Lu2O3 and Lu2(SO4)3. [1] Aqueous solutions of most lutetium salts are colorless and form white crystalline solids upon drying, with the common exception of the iodide. The soluble salts, such as nitrate, sulfate and acetate form hydrates upon crystallization. The oxide, hydroxide, fluoride, carbonate, phosphate and oxalate are insoluble in water. [2]

Contents

Oxides

Lutetium(III) oxide Lutetium(III) oxide sample.jpg
Lutetium(III) oxide

Lutetium(III) oxide is a white solid, a cubic compound of lutetium which sometimes used in the preparation of specialty glasses. It is also called lutecia. It is a lanthanide oxide, also known as a rare earth. [3] [4] [5] Lutetium(III) oxide is an important raw material for laser crystals. [6] It also has specialized uses in ceramics, glass, phosphors, and lasers. Lutetium(III) oxide is used as a catalyst in cracking, alkylation, hydrogenation, and polymerization. [3] The band gap of lutetium oxide is 5.5 eV. [7]

Halides

Lutetium(III) fluoride can be produced by reacting lutetium oxide with hydrogen fluoride, or reacting lutetium chloride and hydrofluoric acid. [8] It can also be produced by reacting lutetium sulfide and hydrofluoric acid: [9]

3 Lu
2S
3+ 20 HF + (2 + 2x) H
2O → 2 (H
3O)Lu
3F
10·xH
2O↓ + 9 H
2S↑ (x = 0.9)
(H3O)Lu3F10 → 3 LuF3 + HF↑ + H2O↑

Lutetium oxide and nitrogen trifluoride react at 240 °C to produce LuOF. A second step happens below 460 °C to produce LuF3. [10] Lutetium(III) chloride forms hygroscopic white monoclinic crystals [11] and also a hydroscopic hexahydrate LuCl3·6H2O. [12] Anhydrous lutetium(III) chloride has the YCl3 (AlCl3) layer structure with octahedral lutetium ions. [13] Lutetium(III) bromide can be synthesized through the following reaction: [14]

2 Lu(s) + 3 Br2(g) → 2 LuBr3(s)

If burned, lutetium(III) bromide may produce hydrogen bromide and metal oxide fumes. [15] Lutetium(III) bromide reacts to strong oxidizing agents. [15] Lutetium(III) iodide can be obtained by reacting lutetium with iodine: [16] [17]

2 Lu + 3 I2 → LuI3

Lutetium(III) iodide can also obtained by the reacting metallic lutetium with mercury iodide in vacuum at 500 °C: [16]

2 Lu + 3 HgI2 → 2 LuI3 + 3 Hg

The elemental mercury generated in the reaction can be removed by distillation. [18] The lutetium(III) iodide hydrate crystallized from the solution can be heated with ammonium iodide to obtain the anhydrate. [19] [16]

Coordination compounds

Nitrogen-containing ligand complexes

Lutetium phtalocyanine

Skeletal formula of lutetium phthalocyanine. LuPc2.svg
Skeletal formula of lutetium phthalocyanine.

Lutetium phthalocyanine is the most notable coordination compound of lutetium, and is derived from lutetium and two phthalocyanines. It was the first known example of a molecule that is an intrinsic semiconductor. [20] [21] It exhibits electrochromism, changing color when subject to a voltage. It is a double-decker sandwich compound consisting of a Lu3+ ion coordinated to two the conjugate base of two phthalocyanines. The rings are arranged in a staggered conformation. The extremities of the two ligands are slightly distorted outwards. [22] The complex features a non-innocent ligand, in the sense that the macrocycles carry an extra electron. [23] It is a free radical [20] with the unpaired electron sitting in a half-filled molecular orbital between the highest occupied and lowest unoccupied orbitals, allowing its electronic properties to be finely tuned. [22] It, along with many substituted derivatives like the alkoxy-methyl derivative Lu[(C8H17OCH2)8Pc]2, can be deposited as a thin film with intrinsic semiconductor properties; [23] said properties arise due to its radical nature [20] and its low reduction potential compared to other metal phthalocyanines. [21] This initially green film exhibits electrochromism; the oxidized form LuPc+
2 is red, whereas the reduced form LuPc−
2 is blue and the next two reduced forms are dark blue and violet, respectively. [23] The green/red oxidation cycle can be repeated over 10,000 times in aqueous solution with dissolved alkali metal halides, before it is degraded by hydroxide ions; the green/blue redox degrades faster in water. [23]

Other complexes

[LuI2(HOiPr)4]I can be dissolved in pyridine-THF to give yellow [LuI(OiPr)(py)5]I. LuI3 is directly dissolved in pyridine-THF to obtain yellow [LuI2(py)5]I. In both compounds pyridine is coordinated to lutetium by nitrogen atom. [24] Lutetium(III) nitrate can be crystallized with 2,2':6',2-terpyridine (terpy) in dry acetonitrile to obtain colorless [Lu(terpy)(NO3)3], in which the nitrogen atom and the oxygen atom of the nitrate are coordinated to the lutetium atom. [25]

Oxygen-containing ligand complexes

In the lutetium(III) acetylacetonate molecule, the acetylacetonate anion acts as a ligand to coordinate with lutetium(III) Lu(acac)3(H2O)2.svg
In the lutetium(III) acetylacetonate molecule, the acetylacetonate anion acts as a ligand to coordinate with lutetium(III)

Trivalent lutetium and water can form complex ions such as [Lu(OH2)n]3+, and lutetium(III) perchlorate and lutetium(III) trifluoromethanesulfonate can exist in the form of hydrates. [26] Ether (R2O) is also a common oxygen-containing ligand. For example, Lu(CH2SiMe3)3(THF)2 can be obtained by reacting lutetium(III) chloride and (trimethylsilyl)methyllithium in a solvent containing tetrahydrofuran (THF). [27]

Other compounds

Adding ammonia water or a hydroxide to the aqueous solution of any soluble lutetium salt can precipitate lutetium(III) hydroxide (Lu(OH)3). The hexagonal lutetium hydroxide can be heated and dehydrated to obtain the monoclinic lutetium oxyhydroxide (LuO(OH)), and further heating will make it decompose into lutetium(III) oxide (Lu2O3). [28] Lutetium oxyhalides (LuOX, X=Cl, Br, I) can be obtained by hydrolysis of the lutetium trihalides. [28] Lu2Cl2C can be obtained by reacting lutetium(III) chloride, caesium chloride, lutetium and carbon at a high temperature. [29]

Related Research Articles

The lanthanide or lanthanoid series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium is also sometimes considered a lanthanide, despite being a d-block element and a transition metal.

<span class="mw-page-title-main">Californium compounds</span>

Few compounds of californium have been made and studied. The only californium ion that is stable in aqueous solutions is the californium(III) cation. The other two oxidation states are IV (strong oxidizing agents) and II (strong reducing agents). The element forms a water-soluble chloride, nitrate, perchlorate, and sulfate and is precipitated as a fluoride, oxalate or hydroxide. If problems of availability of the element could be overcome, then CfBr2 and CfI2 would likely be stable.

<span class="mw-page-title-main">Berkelium compounds</span> Chemical compounds

Berkelium forms a number of chemical compounds, where it normally exists in an oxidation state of +3 or +4, and behaves similarly to its lanthanide analogue, terbium. Like all actinides, berkelium easily dissolves in various aqueous inorganic acids, liberating gaseous hydrogen and converting into the trivalent oxidation state. This trivalent state is the most stable, especially in aqueous solutions, but tetravalent berkelium compounds are also known. The existence of divalent berkelium salts is uncertain and has only been reported in mixed lanthanum chloride-strontium chloride melts. Aqueous solutions of Bk3+ ions are green in most acids. The color of the Bk4+ ions is yellow in hydrochloric acid and orange-yellow in sulfuric acid. Berkelium does not react rapidly with oxygen at room temperature, possibly due to the formation of a protective oxide surface layer; however, it reacts with molten metals, hydrogen, halogens, chalcogens and pnictogens to form various binary compounds. Berkelium can also form several organometallic compounds.

<span class="mw-page-title-main">Thorium compounds</span> Chemical compounds

Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.

<span class="mw-page-title-main">Lutetium(III) fluoride</span> Chemical compound

Lutetium(III) fluoride is an inorganic compound with a chemical formula LuF3.

Praseodymium compounds are compounds formed by the lanthanide metal praseodymium (Pr). In these compounds, praseodymium generally exhibits the +3 oxidation state, such as PrCl3, Pr(NO3)3 and Pr(CH3COO)3. However, compounds with praseodymium in the +2 and +4 oxidation states, and unlike other lanthanides, the +5 oxidation state, are also known.

<span class="mw-page-title-main">Neodymium(II) iodide</span> Chemical compound

Neodymium(II) iodide or neodymium diiodide is an inorganic salt of iodine and neodymium the formula NdI2. Neodymium uses the +2 oxidation state in the compound.

Einsteinium compounds are compounds that contain the element einsteinium (Es). These compounds largely have einsteinium in the +3 oxidation state, or in some cases in the +2 and +4 oxidation states. Although einsteinium is relatively stable, with half-lives ranging from 20 days upwards, these compounds have not been studied in great detail.

<span class="mw-page-title-main">Europium compounds</span> Chemical compounds

Europium compounds are compounds formed by the lanthanide metal europium (Eu). In these compounds, europium generally exhibits the +3 oxidation state, such as EuCl3, Eu(NO3)3 and Eu(CH3COO)3. Compounds with europium in the +2 oxidation state are also known. The +2 ion of europium is the most stable divalent ion of lanthanide metals in aqueous solution. Many europium compounds fluoresce under ultraviolet light due to the excitation of electrons to higher energy levels. Lipophilic europium complexes often feature acetylacetonate-like ligands, e.g., Eufod.

<span class="mw-page-title-main">Terbium compounds</span> Chemical compounds with at least one terbium atom

Terbium compounds are compounds formed by the lanthanide metal terbium (Tb). Terbium generally exhibits the +3 oxidation state in these compounds, such as in TbCl3, Tb(NO3)3 and Tb(CH3COO)3. Compounds with terbium in the +4 oxidation state are also known, such as TbO2 and BaTbF6. Terbium can also form compounds in the 0, +1 and +2 oxidation states.

<span class="mw-page-title-main">Lanthanum(III) iodide</span> Chemical compound

Lanthanum(III) iodide is an inorganic compound containing lanthanum and iodine with the chemical formula LaI
3.

Protactinium(V) iodide is an inorganic compound, with the chemical formula of PaI5.

Europium(III) iodide is an inorganic compound containing europium and iodine with the chemical formula EuI3.

<span class="mw-page-title-main">Lutetium(III) iodide</span> Chemical compound

Lutetium(III) iodide or lutetium iodide is an inorganic compound consisting of iodine and lutetium, with the chemical formula of LuI3.

Cobalt compounds are chemical compounds formed by cobalt with other elements.

Erbium compounds are compounds containing the element erbium (Er). These compounds are usually dominated by erbium in the +3 oxidation state, although the +2, +1 and 0 oxidation states have also been reported.

Ytterbium compounds are chemical compounds that contain the element ytterbium (Yb). The chemical behavior of ytterbium is similar to that of the rest of the lanthanides. Most ytterbium compounds are found in the +3 oxidation state, and its salts in this oxidation state are nearly colorless. Like europium, samarium, and thulium, the trihalides of ytterbium can be reduced to the dihalides by hydrogen, zinc dust, or by the addition of metallic ytterbium. The +2 oxidation state occurs only in solid compounds and reacts in some ways similarly to the alkaline earth metal compounds; for example, ytterbium(II) oxide (YbO) shows the same structure as calcium oxide (CaO).

Protactinium compounds are compounds containing the element protactinium. These compounds usually have protactinium in the +5 oxidation state, although these compounds can also exist in the +2, +3 and +4 oxidation states.

Americium compounds are compounds containing the element americium (Am). These compounds can form in the +2, +3, and +4, although the +3 oxidation state is the most common. The +5, +6 and +7 oxidation states have also been reported.

References

  1. ↑ "Lutetium".
  2. ↑ Patnaik, Pradyot (2003). Handbook of Inorganic Chemical Compounds. McGraw-Hill. p. 510. ISBN   978-0-07-049439-8 . Retrieved 2009-06-06.
  3. 1 2 Lutetium Oxide. 1997-2007. Metall Rare Earth Limited. http://www.metall.com.cn/luo.htm
  4. ↑ Macintyre, J. E. (1992). Dictionary of Inorganic Compounds Volumes 1–3. London: Chapman & Hall.
  5. ↑ Trotman-Dickenson, A. F. (1973). Comprehensive Inorganic Chemistry. Oxford: Pergamon.
  6. ↑ Parsonage, Tina L.; Beecher, Stephen J.; Choudhary, Amol; Grant-Jacob, James A.; Hua, Ping; MacKenzie, Jacob I.; Shepherd, David P.; Eason, Robert W. (2015). "Pulsed laser deposited diode-pumped 7.4 W Yb:Lu2O3 planar waveguide laser" (PDF). Optics Express. 23 (25): 31691–7. Bibcode:2015OExpr..2331691P. doi: 10.1364/oe.23.031691 . PMID   26698962.
  7. ↑ Ordin, S. V.; Shelykh, A. I. (2010). "Optical and dielectric characteristics of the rare-earth metal oxide Lu2O3". Semiconductors. 44 (5): 558–563. Bibcode:2010Semic..44..558O. doi:10.1134/S1063782610050027. S2CID   101643906.
  8. ↑ Georg Brauer (ed.), In collaboration with Marianne Baudler u. a .: Handbook of Preparative Inorganic Chemistry. 3rd, revised edition. Volume I, Ferdinand Enke, Stuttgart 1975, ISBN   3-432-02328-6 , p. 254.
  9. ↑ O.V. Andrrev, I.A. Razumkova, A.N. Boiko (March 2018). "Synthesis and thermal stability of rare earth compounds REF 3 , REF 3 · n H 2 O and (H 3 O)RE 3 F 10 · n H 2 O (RE = Tb − Lu, Y), obtained from sulphide precursors". Journal of Fluorine Chemistry. 207: 77–83. doi:10.1016/j.jfluchem.2017.12.001.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  10. ↑ Randall D. Scheele, Bruce K. McNamara, Andrew M. Casella, Anne E. Kozelisky, Doinita Neiner (February 2013). "Thermal NF3 fluorination/oxidation of cobalt, yttrium, zirconium, and selected lanthanide oxides". Journal of Fluorine Chemistry. 146: 86–97. doi:10.1016/j.jfluchem.2012.12.013.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  11. ↑ Lide, David R. (1998), Handbook of Chemistry and Physics (87 ed.), Boca Raton, Florida: CRC Press, p. 472, ISBN   0-8493-0594-2 , retrieved 2008-06-27
  12. ↑ "Lutetium(III) chloride hexahydrate 542075". Sigma-Aldrich. Retrieved 2019-07-24.
  13. ↑ Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN   0-19-855370-6
  14. ↑ Winter, Mark. "Lutetium»reactions of elements [WebElements Periodic Table]". www.webelements.com. Retrieved 22 December 2016.
  15. 1 2 "Lutetian bromide" (PDF). SDS. Retrieved 22 December 2016.
  16. 1 2 3 Georg Brauer (Hrsg.), unter Mitarbeit von Marianne Baudler u. a.: Handbuch der Präparativen Anorganischen Chemie. 3., umgearbeitete Auflage. Band I, Ferdinand Enke, Stuttgart 1975, ISBN 3-432-02328-6, S. 1077.
  17. ↑ Webelements: Lutetium: lutetium triiodide Retrieved 31.3.2018
  18. ↑ Asprey, L. B.; Keenan, T. K.; Kruse, F. H. Preparation and crystal data for lanthanide and actinide triiodides. Inorg. Chem., 1964. 3 (8): 1137-1240
  19. ↑ 无机化学丛书 第七卷 钪 稀土元素. 科学出版社. pp 211
  20. 1 2 3 Belarbi, Z.; Sirlin, C.; Simon, J.; Andre, Jean Jacques (November 1989). "Electrical and magnetic properties of liquid crystalline molecular materials: lithium and lutetium phthalocyanine derivatives". The Journal of Physical Chemistry. 93 (24): 8105–8110. doi:10.1021/j100361a026.
  21. 1 2 Trometer, M.; Even, R.; Simon, J.; Dubon, A.; Laval, J.-Y.; Germain, J.P.; Maleysson, C.; Pauly, A.; Robert, H. (May 1992). "Lutetium bisphthalocyanine thin films for gas detection". Sensors and Actuators B: Chemical. 8 (2): 129–135. doi:10.1016/0925-4005(92)80169-X.
  22. 1 2 Bidermane, I.; Lüder, J.; Boudet, S.; Zhang, T.; Ahmadi, S.; Grazioli, C.; Bouvet, M.; Rusz, J.; Sanyal, B.; Eriksson, O.; Brena, B.; Puglia, C.; Witkowski, N. (21 June 2013). "Experimental and theoretical study of electronic structure of lutetium bi-phthalocyanine". The Journal of Chemical Physics. 138 (23): 234701. Bibcode:2013JChPh.138w4701B. doi:10.1063/1.4809725. ISSN   0021-9606. PMID   23802970.
  23. 1 2 3 4 Toupance, Thierry; Plichon, Vincent; Simon, Jacques (1999). "Substituted bis(phthalocyanines): electrochemical properties and probe beam deflection (mirage) studies". New Journal of Chemistry. 23 (10): 1001–1006. doi:10.1039/A905248H.
  24. ↑ Garth R. Giesbrecht, John C. Gordon, David L. Clark, Brian L. Scott (2004-02-01). "Auto-ionization in Lutetium Iodide Complexes: Effect of the Ionic Radius on Lanthanide−Iodide Binding". Inorganic Chemistry. 43 (3): 1065–1070. doi:10.1021/ic035090y. ISSN   0020-1669. PMID   14753829 . Retrieved 2022-12-29.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  25. ↑ Birte Ahrens, Simon A. Cotton, Neil Feeder, Oliver E. Noy, Paul R. Raithby, Simon J. Teat (2002-04-26). "Structural variety in nitrate complexes of the heavy lanthanides with 2,2′:6′,2″-terpyridine, and stereoselective replacement of nitrate". Journal of the Chemical Society, Dalton Transactions (9): 2027–2030. doi:10.1039/b200480c . Retrieved 2022-12-29.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  26. ↑ Simon A. Cotton, Paul R. Raithby, Alexander Shield, Jack M. Harrowfield (March 2022). "A comparison of the structural chemistry of scandium, yttrium, lanthanum and lutetium: A contribution to the group 3 debate". Coordination Chemistry Reviews. 455: 214366. doi:10.1016/j.ccr.2021.214366. S2CID   245712597 . Retrieved 2022-12-29.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  27. ↑ Konstantin A. Rufanov, Dominique M. M. Freckmann, Heinz-Jürgen Kroth, Stefan Schutte, Herbert Schumann (2005-05-01). "Studies on the Thermolysis of Ether-Stabilized Lu(CH 2 SiMe 3 ) 3 . Molecular Structure of Lu(CH 2 SiMe 3 ) 3 (THF)(diglyme)". Zeitschrift für Naturforschung B. 60 (5): 533–537. doi: 10.1515/znb-2005-0509 . ISSN   1865-7117. S2CID   100903579.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  28. 1 2 无机化学丛书. pp 206. 1.3.3 氧化态+3的化合物.
  29. ↑ Thomas Schleid, Gerd Meyer (September 1987). "Synthesis and crystal structures of hydrogen and carbon stabilized lutetium monochloride, LuClHx and Lu2Cl2C". Zeitschrift für anorganische und allgemeine Chemie (in German). 552 (9): 90–96. doi:10.1002/zaac.19875520909. ISSN   0044-2313 . Retrieved 2022-12-29.
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