Transition metal tetraperoxide complexes

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Structure of the .mw-parser-output .template-chem2-su{display:inline-block;font-size:80%;line-height:1;vertical-align:-0.35em}.mw-parser-output .template-chem2-su>span{display:block;text-align:left}.mw-parser-output sub.template-chem2-sub{font-size:80%;vertical-align:-0.35em}.mw-parser-output sup.template-chem2-sup{font-size:80%;vertical-align:0.65em} [Ti(O2)4] ion. 208758-ICSD.png
Structure of the [Ti(O2)4] ion.

Transition metal tetraperoxide complexes are coordination complexes with the formula [M(O2)4]n-. They all feature 8-coordinate metal centers with four side-bonded peroxide ligands. The O-O distances, which are near 150 picometers, indicate O22-. They are prepared by reaction of the metal oxides with an alkaline solution of hydrogen peroxide. [1]

Examples, by triad

Titanium-peroxide complexes have long been the basis of a colorimetric test for peroxide. [2] The orange salts [M'4M(O2)4] are known for M' = Li, Na, K. [1]

Tetraperoxides of the vanadium triad are well established; all feature metals in their highest oxidation states. Salts of vanadium(V) tetraperoxide trianion, which is blue, have long been known since the 19th century following investigations of the reaction of hydrogen peroxide with vanadium pentoxide. [3] The salt Rb3Nb(O2)4 [4] and K3Ta(O2)4 (colorless) have also been verified by X-ray crystallography. [5]

Turning to the tetraperoxides of the group VI metals, the most distinctive complex is [Cr(O2)4]3−, which features the d1 ion Cr(V). [6] The metals centers in all other tetraperoxides have the d0 electronic configuration. Many salts are known. Early evidence for polyperoxides of Mo and W was obtained by Raman spectroscopy, which is sensitive for the O-O vibration near 800 cm-1. [7] This work was followed by crystallographic confirmation of the alkali metal salts of [Mo(O2)4]2− and [W(O2)4]2−, which are red and yellow, respectively. [8] [9] [10]

References

  1. 1 2 3 Bach, Karlie; Garrido Ribó, Eduard; Hirschi, Jacob S.; Mao, Zhiwei; Nord, Makenzie T.; Zakharov, Lev N.; Goulas, Konstantinos A.; Zuehlsdorff, Tim J.; Nyman, May (2025). "Tetraperoxotitanates for High-Capacity Direct Air Capture of Carbon Dioxide". Chemistry of Materials. 37: 48–61. doi:10.1021/acs.chemmater.4c01795.
  2. ↑ Hossain, Rayhan; Dickinson, Jimmy J.; Apblett, Allen; Materer, Nicholas F. (2022). "Detection of Hydrogen Peroxide in Liquid and Vapors Using Titanium(IV)-Based Test Strips and Low-Cost Hardware". Sensors. 22 (17): 6635. Bibcode:2022Senso..22.6635H. doi: 10.3390/s22176635 . PMC   9460035 . PMID   36081093.
  3. ↑ Schwendt, Peter; Tatiersky, Jozef; Krivosudský, Lukáš; Šimuneková, Mária (2016). "Peroxido Complexes of Vanadium". Coordination Chemistry Reviews. 318: 135–157. doi:10.1016/j.ccr.2016.03.011.
  4. ↑ Haeuseler, H.; Wagener, M.; Müller, H. (1997). "Darstellung, Kristallstruktur und Schwingungsspektren von Rubidiumperoxoniobat (Rb3NbO8)". Zeitschrift für Naturforschung B. 52 (9): 1082–1086. doi:10.1515/znb-1997-0912.
  5. ↑ Wehrum, G.; Hoppe, R. (1993). "Zur Konstitution von Alkaliperoxotantalaten(V): Über den Aufbau von K3[Ta(O2)4]". Zeitschrift für Anorganische und Allgemeine Chemie. 619 (7): 1315–1320. doi:10.1002/zaac.19936190727.
  6. ↑ Sergienko, V. S. (2007). "Structural chemistry of peroxo compounds of group VI transition metals: I. Peroxo Complexes of Chromium". Crystallography Reports. 52 (4): 639–646. Bibcode:2007CryRp..52..639S. doi:10.1134/S1063774507040116. S2CID   95018505.
  7. ↑ Campbell, Nicholas J.; Dengel, Andrew C.; Edwards, Catherine J.; Griffith, William P. (1989). "Studies on transition metal peroxo complexes. Part 8. The nature of peroxomolybdates and peroxotungstates in aqueous solution". Journal of the Chemical Society, Dalton Transactions (6): 1203. doi:10.1039/DT9890001203.
  8. ↑ Grzywa, M.; Łasocha, W.; Rutkowska-Żbik, D. (2009). "Structural investigation of tetraperoxo complexes of Mo(VI) and W(VI)". Journal of Solid State Chemistry. 182 (4): 973–982. doi:10.1016/j.jssc.2009.01.009.
  9. ↑ Grzywa, M.; Nitek, W.; Łasocha, W. (2007). "Synthesis, characterization and crystal structures of lithium tetraperoxomolybdate(VI) tetrahydrate Li2[Mo(O2)4]·4H2O and lithium tetraperoxotungstate(VI) tetrahydrate Li2[W(O2)4]·4H2O". Journal of Molecular Structure. 828 (1–3): 111–115. Bibcode:2007JMoSt.828..111G. doi:10.1016/j.molstruc.2006.05.043.
  10. ↑ Grzywa, M.; Różycka, M.; Łasocha, W. (2005). "Crystal Structure of Potassium Tetraperoxomolybdate (VI) K2[Mo(O2)4]". Powder Diffraction. 20 (3): 203–206. doi:10.1154/1.1997170.
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