Abstract
Stereochemistry and redox property are essential factors in considering the roles of vanadium in biological systems. Coordination geometries adopted by vanadium ions with oxidation numbers +3, +4, and +5 are summarized in this chapter to provide a clue for determining the structure-function relationship of biological vanadium species. Vanadium can have a variety of geometries and its geometry is sometimes flexible. This property may be important for metals in biological systems. The electrochemical properties of complexes in each oxidation state are described by referring to typical mononuclear complexes. The redox potentials of the complexes depend largely on the ligand combination. A comparison of complexes with and without oxo ligands reveals that strong electron donation from oxo ligands stabilizes vanadium ions in higher oxidation states. Additionally, the proton-coupled equilibrium between oxo and aqua ligands imposes a significant effect on the redox behavior of vanadium complexes. Chemical redox reactions related to vanadium catalysts are also described.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Similar content being viewed by others
References
Atkins P, Overton T, Rourke J, Weller M, Armstrong F (2006) Shriver & Atkins inorganic chemistry, 4th edn. Oxford University Press, Oxford
Fenton DE (1995) Biocoordination chemistry. Oxford University Press, Oxford
Elvington K, Gonzalez A, Pettersson L (1996) Speciation in vanadium bioinorganic systems. 2. An NMR, ESR, and potentiometric study of the aqueous H+–vanadate–maltol system. Inorg Chem 35:3388–3393
Rehder D (2008) Bioinorganic vanadium chemistry. Wiley, Chichester
Choukroun R, Moumboko P, Chevalier S, Etienne M, Donnadieu B (1998) Cationic homoleptic vanadium(II), (IV), and (V) complexes arising from protonolysis of [V(NEt)4]. Angew Chem Int Ed 37:3169–3172
Dubberley SR, Tyrell BR, Mountford P (2001) Tetrakis(dimethylamido)vanadium(IV). Acta Cryst C57:902–904
Song JI, Gambarotta S (1996) Preparation, characterization, and reactivity of a diamagnetic vanadium nitride. Chem Eur J 2:1258–1263
Komuro T, Matsuo T, Kawaguchi H, Tatsumi K (2005) Synthesis of a vanadium(III) tris(arylthiolato) complex and its reactions with azide and azo compounds: formation of a sulfenamide complex via cleavage of an azo N=N bond. Inorg Chem 44:175–177
Messerschmidt A, Wever R (1996) X-ray structure of a vanadium-containing enzyme: chloroperoxidase from the fungus Curvularia inaequalis. Proc Natl Acad Sci USA 93: 392–396
Messerschmidt A, Prade L, Wever R (1997) Implications for the catalytic mechanisms of the vanadium-containing enzyme chloroperoxidase from the fungus Curvularia inaequalis by X-ray structures of the native and peroxide form. Biol Chem 378:309–315
Addison AW, Rao TN, Reedijk J, Jacobus VR, Verschoor GC (1984) Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulfur donor ligands: the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidzol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate. J Chem Soc Dalton Trans 1349–1356
Baruah B, Rath SP, Chakravorty A (2004) A novel pentacoordinated dioxovanadium(V) salicylaldiminate: solvent specific crystallization of dimorphs with contrasting coordination geometries, ligand conformations and supramolecular architectures. Eur J Chem 9: 1873–1878
Cornman CR, Geiser-Bush KM, Rowley SP, Boyle PD (1997) Structural and electron paramagnetic resonance studies of the square pyramidal to trigonal bipyramidal distortion of vanadyl complexes containing sterically crowded Schiff base ligands. Inorg Chem 36:6401–6408
Wikete C, Wu P, Zampella G, De Giola L, Licini G, Rehder D (2007) Glycine-and sarcosine-based models of vanadium-dependent haloperoxidases in sulfoxygenation reactions. Inorg Chem 46:196–207
Santoni G, Licini G, Rehder D (2003) Catalysis of oxo transfer to prochiral sulfides by oxovanadium(V) compounds that model the active center of haloperoxidases. Chem Eur J 9:4700–4708
Hsu HF, Chu WC, Hung CH, Liao JH (2003) The first example of a seven-coordinate vanadium(III) thiolate complex containing the hydrazine molecule, an intermediate of nitrogen fixation. Inorg Chem 42:7369–7371
Groysman S, Goldberg I, Goldschmidt Z, Kol M (2005) Vanadium(III) and vanadium(V) amine tris(Phenolate) complexes. Inorg Chem 44:5073–5080
Aghabozorg H, Sadr-khanlou E (2007) 2,9-Dimethyl-1,10-phenanthrolinium dioxo(pyridine-2,6-dicarboxylato)vanadate(V) Monohydrate. Acta Cryst E63:m1753
Nakajima K, Tokida N, Kojima M, Fujita J (1992) Structures of two geometrical isomers of dioxo[(S)-N-salicylidene-3-aminopyrrolidine]vanadium(V). Bull Chem Soc Jpn 65:1725–1727
Santoni G, Rehder D (2003) Structural models for the reduced form of vanadate-dependent peroxidases: vanadyl complexes with bidentate chiral Schiff base ligands. J Inorg Biochem 98:758–764
Lorber C, Choukroun R, Donnadieu B (2003) Synthesis and crystal structure of unprecedented phosphine adducts of d1-aryl imido–vanadium(IV) complexes. Inorg Chem 42:673–675
Stiefel EI, Eisenberg R, Rosenberg RC, Gray HB (1966) Characterization and electronic structures of six-coordinate trigonal-prismatic complexes. J Am Chem Soc 88:2956–2966
Kondo M, Minakoshi S, Iwata K, Shimizu T, Matsuzaka H, Kamigata N, Kitagawa S (1996) Crystal structure of a tris(dithiolene) vanadium(IV) complex having unprecedented D 3h symmetry. Chem Lett 25:489–490
Eisenberg R, Stiefel EI, Rosenberg RC, Gray HB (1966) Six-coordinate trigonal-prismatic complexes of first-row transition metals. J Am Chem Soc 88:2874–2876
Welch JH, Bereman RD, Singh P (1988) Synthesis and characterization of two vanadium complexes of the 1,2-dithiolene 5,6-dihydro-1,4-dithiin-2,3-dithiolate. Crystal structure of [(C4H9)4N][V(DDDT)3]. Inorg Chem 27:2862–2868
Stiefel EI, Dori Z, Gray HB (1967) Octahedral vs. trigonal-prismatic coordination. Structure of (Me4N)2[V(mnt)3]. J Am Chem Soc 89:3353–3354
Cooper SR, Koh YB, Raymond KN (1982) Synthetic, structural, and physical studies of bis(triethylammonium) tris(catecholato)vanadate(IV), potassium bis(catecholato) oxovanadate(IV), and potassium tris(catecholato)vanadate(III). J Am Chem Soc 104:5092–5102
Branca M, Micera G, Dessi A, Sanna D, Raymond KN (1990) Formation and structure of the tris(catecholato)vanadate(IV) complex in aqueous solution. Inorg Chem 29:1586–1589
Cass ME, Gordon NR, Pierpont CG (1986) Catecholate and semiquinone complexes of vanadium. Factors that direct charge distribution in metal–quinone complexes. Inorg Chem 25:3962–3967
Kanamori K, Kusajima K, Yachi H, Suzuki H, Miyashita Y, Okamoto K (2007) Synthesis, x-ray structures, and solution properties of vanadium(III) and –(IV) complexes with N-(2-hydroxyphenyl)-N-(2-pyridylmethyl)amine. Bull Chem Soc Jpn 80:324–328
Morgenstern B, Steinhauser S, Hogetschweiler K, Garribba E, Micera G, Sanna D, Nagy L (2004) Complex formation of vanadium(IV) with 1,3,5-triamino-1,3,5-trideoxy-cis-inositol and related ligands. Inorg Chem 43:3116–3126
Drew RE, Einstein FWB (1972) The crystal structure of ammonium oxodiperoxoamminevanadate(V). Inorg Chem 11:1079–1083
Crans DC, Keramidas AD, Hoover-Litty H, Anderson OP, Miller MM, Lemoine LM, Pleasic-Williams S, Vandenberg M, Rossomando AJ, Sweet LJ (1997) Synthesis, structure, and biological activity of a new insulinomimetic peroxovanadium compound: bisperoxovanadium imidazole monoanion. J Am Chem Soc 119:5447–5448
Smatanová IK, Marek J, Švančárek P, Schwendt P (2000) Bis(tetra-n-butylammonium) bis[(mandelato)oxo(peroxo)vanadate(V)] mandelic acid solvate. Acta Cryst C56:154–155
(a) Towns RLR, Levenson RA (1972) Structure of the seven-coordinate cyano complex of vanadium(III). J Am Chem Soc 94:4345–4346. (b) Levenson RA, Towns RLR (1974) Crystal and molecular structure of potassium heptacyanovanadate(III) dihydrate. Inorg Chem 13: 105–109
Neumann R, Assael I (1989) Vanadium(V)/vanadium(III) redox couple in acidic organic media. Structure of a vanadium(III)-tetraethylene glycol pentagonal-bipyramidal complex [[V(teg)(Br)2]+Br−]. J Am Chem Soc 111:8410–8413
Dutton JC, Fallon GD, Murray KS (1990) A macrocyclic binuclear vanadium(III) complex with di-µ-alkoxo bridging and pentacoordinate-bipyramidal metal co-ordination. X-ray crystal structure of [V2L(H2O)4][ClO4]4·2H2O (H2L = 1,7,14,20-tetramethyl-2,6,15,19-tetra-aza[7,7](2,6)-pyridinophane-4,7-diol). J Chem Soc Chem Commun 64–65
Stomberg R (1986) The crystal structure of potassium bis(oxalate)oxoperoxovanadate(V) hemihydrate, K3[VO(O2)(C2O4)]·½H2O, and potassium bis(oxalate)dioxovanadate(V) trihydrate, K3[VO2(C2O4)2]·3H2O. Acta Chem Scand A40:168–176
Gyepes R, Pacigová S, Sivák M, Tatiersky J (2009) Experimental and computational evidence of solid-state anion–π and π–π interactions in [VO(O2)(L)(pa)]·xH2O complexes (L = picolinate, pyrazinate or quinolinate; pa = picolinamide). New J Chem 33:1515–1522
Szentivanyi H, Stomberg R (1983) The crystal structure of ammonium (2,2′-bipyridine) oxodiperoxovanadate(V) tetrahydrate, NH4[VO(O2)2(C10H8N2)]·4H2O, at –100°C. Acta Chem Scand A37:553–559
Castro SL, Martin JD, Christou G (1993) A new vanadium(V) persulfide complex: (NEt4)[VO(S2)2(bpy)]. Inorg Chem 32:2978–2980
Al-Ani FT, Hughes DL, Pickett CJ (1988) Preparation, x-ray crystal structure, and properties of [V(S2)2(terpy)]: intramolecular coupling of the sulfide ligands of [VS4]3-. J Chem Soc Dalton Trans 1705–1707
Einstein FEB, Enwall E, Morris DM, Sutton D (1971) Crystal and molecular structure and vibrational spectra of the vanadium(V) oxide trinitrate–acetonitrile complex, VO(NO3)3·CH3CN. Inorg Chem 10:678–686
Kanamori K, Kameda E, Okamoto K (1996) Heptacoordinate vanadium(III) complexes containing a didentate sulfate ligand. X-ray structures of [V2(SO4)3{N, N′-bis(2-pyridylmethyl)-1,2-ethanediamine}2] and [V(SO4){N, N, N′, N′-tetrakis(2-pyridylmethyl)-1,2-ethanediamine}]+ and their solution properties. Bull Chem Soc Jpn 69:2901–2909
Chatterjee M, Maji M, Ghosh S, Mak TCW (1998) Studies of V(III) complexes with selected α-N-heterocyclic carboxylato NO donor ligands: structure of a new seven-coordinated pentagonal bipyramidal complex containing picolinato ligands. J Chem Soc Dalton Trans 3641–3645
Okamoto K, Hidaka J, Fukagawa M, Kanamori K (1992) Structure of trisaqua (nitrilotriacetato)vanadium(III) tetrahydrate. Acta Cryst C48:1025–1027
Shimoi M, Saito Y, Ogino H (1991) Syntheses and crystal structures of seven-coordinate (ethylenediamine-N, N, N′, N′-tetraacetato)aquavanadate(III) complexes. Bull Chem Soc Jpn 64:2629–2634
Ogino H, Shimoi M, Saito Y (1989) Structural identification of the reactive vanadium(III) intermediate formed in the electron-transfer reactions of [N′-(2-hydroxyethyl)ethylenediamine-N, N, N′-triacetato]aquavanadium(III) complex ([V(hedtra)(H2O)]) with halogenopentaamminecobalt(III) complex: x-ray crystal structure of [V(hedtra)(H2O)]·2H2O and K[VO(hedtra)]·H2O. Inorg Chem 28:3596–3600
Miyoshi K, Wang J, Mizuta T (1995) An x-ray crystallographic study on the molecular structures of seven-coordinate (ethylenediamine-N, N, N′-triacetato-N′-acetic acid)(aqua)-titanium(III) and -vanadium(III), [TiIII(hedta)(H2O)]·H2O and [VIII(hedta)(H2O)]·H2O. Inorg Chim Acta 228:165–172
Kanamori K, Kyotoh A, Fujimoto K, Nagata K, Suzuki H, Okamoto K (2001) Syntheses, structures, and properties of vanadium(III) complexes with the hexadentate ligand, tetramethylenediamine-N, N, N′, N′-tetraacetate, N, N′-bis(2-pyridylmethyl)-1,2-ethanediamine-N, N′-diacetate, and N, N′-bis(2-pyridylmethyl)-1,3-propanediamine-N, N′-diacetate. Bull Chem Soc Jpn 74:2113–2118
Kanamori K, Ino K, Maeda H, Miyazaki K, Fukagawa M, Kumada J, Eguchi T, Okamoto K (1994) Relationship between oxo-bridged dimer formation and structure of vanadium(III) amino polycarboxylates. Inorg Chem 33:5547–5554
Kanamori K, Yamamoto K, Okayasu T, Matsui N, Okamoto K, Mori W (1997) Structure and magnetic properties of dinuclear vanadium(III) complexes with alkoxo bridge. Bull Chem Soc Jpn 70:3031–3040
Kanamori K, Okayasu T, Okamoto K (1995) Preparation and structure of dinuclear vanadium(III) complex triply bridged by three different groups. Chem Lett 24:105–106
Berry RE, Armstrong EM, Beddoes RL, Collison D, Ertok SN, Helliwell M, Garner CD (1999) The structural characterization of amavadin. Angew Chem Int Ed 38:795–797
Armstrong EM, Beddoes RL, Calviou LJ, Charnock JM, Collison D, Ertok N, Naismith JH, Garner CD (1993) The chemical nature of amavadin. J Am Chem Soc 115:807–808
Carrond MAAFdeCT, Duarte MTLS, Costa Pessoa J, Silva JAL, Fraústo da Silva JJR, Candida M, Vaz TA, Vilas-Boas LF (1988) Bis(N-hydroxyiminodiacetate)vanadate(IV), a synthetic model of amavadin. J Chem Soc Chem Commun 17:1158–1159
Won TJ, Barnes CL, Schlemper EO, Thompson RC (1995) Two crystal structures featuring the tetraperoxovanadate(V) anion and a brief reinvestigation of peroxovanadate equilibria in neutral and basic solution. Inorg Chem 34:4499–4503
Piovesana O, Cappuccilli G (1972) Eight-coordination. I. Dodecahedral vanadium(IV) complexes with sulfur-chelating ligands. Inorg Chem 11:1543–1550
Fanfani L, Nunzi A, Zanazzi PF, Zanzari AR (1972) The crystal structure of tetrakis(dithioacetato)vanadium(IV). Acta Cryst B28:1298–1302
Bonamico M, Dessy G, Fares V, Scaramuzza L (1974) Structural studies of eight-co-ordinate metal complexes. Part I. Crystal and molecular structures of tetrakis (phenylthioacetato)vanadium(IV) and tetrakis(dithiobenzoato)vanadium(IV). J Chem Soc Dalton Trans 1258–1263
Sendlinger SC, Nicholson JR, Lobkovsky EB, Hufman JC, Rehder D, Christou G (1993) Reactivity studies of mononuclear and dinuclear vanadium–sulfide–thiolate compounds. Inorg Chem 32:204–210
Duraj SA, Andras MT, Kibala PA (1990) Metal–metal bonds involving vanadium atoms. A facile synthesis of a novel divanadium tetrakis(dithioacetate) that contains two µ-η2-S2 bridges from bis(benzene)vanadium(0) and dithioacetic acid. Inorg Chem 29:1232–1234
Cotton FA, Wilkinson G, Bochmann M, Murillo C (1998) Advanced inorganic chemistry, 6th edn. Wiley, New York
Shaw MJ (2006) Vanadium electrochemistry. Encyclopedia of electrochemistry, vol 7a. Wiley, Weinheim, pp 357–381
Pampaloni G, Koelle U (1994) Chemical and electrochemical studies on metal carbonyl/cobaltocene Systems. J Organomet Chem 481:1–6
Elschenbroich C, Kroker J, Nowotny M, Behrendt A, Metz B, Harms K (1999) η6-coordination of arsenine to titanium, vanadium, and chromium. Organometallics 18:1495–1503
Dobson JC (1989) Coordination chemistry and redox properties of polypyridyl complexes of vanadium(II). Inorg Chem 28:1310–1315
Ghosh P, Taube H, Hasegawa T, Kuroda R (1995) Vanadium(II) salts in pyridine and acetonitrile solvents. Inorg Chem 34:5761–5775
Holloway JDL, Geiger WE Jr (1979) Electron-transfer reactions of metallocenes. Influence of metal oxidation state on structure and reactivity. J Am Chem Soc 101:2038–2044
Ogino H, Nagata T, Ogino K (1989) Redox potentials and related thermodynamic parameters of (diaminopolycarboxylato)metal(III/II) redox couples. Inorg Chem 28:3656–3659
Sokolowski A, Adam B, Weyhermüller T, Kikuchi A, Hildenbrand K, Schnepf R, Hildebrandt P, Bill E, Wieghardt K (1997) Metal- vs. ligand-centered oxidations in phenolato−vanadium and− cobalt complexes: characterization of phenoxyl−cobalt(III) species. Inorg Chem 36:3702–3710
Hawkins CJ, Kabanos TA (1989) Synthesis and characterization of (catecholato)bis (β-diketonato)vanadium(IV) complexes. Inorg Chem 28:1084–1087
Klich PR, Daniher AT, Challen PR, McConville DB, Youngs WJ (1996) Vanadium(IV) complexes with mixed O, S donor ligands. Syntheses, structures, and properties of the anions tris(2-mercapto-4-methylphenolato)vanadate(IV) and bis(2-mercaptophenolato)oxovanadate(IV). Inorg Chem 35:347–356
Best SP, Ciniawsky SA, Humphrey DG (1996) Fourier-transform infrared study of short-lived highly reduced dithiolene complexes by potential-modulation spectroelectrochemical techniques. J Chem Soc Dalton Trans 2945–2949
Nawi MA, Riechel TL (1981) Electrochemical studies of vanadium(III) and vanadium(IV) acetylacetonate complexes in dimethylsulfoxide. Inorg Chem 20:1974–1978
Kabanos TA, Slawin AM, Williams DJ, Woollins JD (1990) The preparation and x-ray structure of V(N3S2)(dtbs)(phen)·CHCl3 (dtbc = di-t-butylcatecholate, phen = phenanthroline). J Chem Soc Chem Commun 193–194
Michibata H, Kanamori K (1998) Selective accumulation of vanadium by ascidians from seawater. Advances in environmental science and technology, vol 30 (Vanadium in the environment, part 1), Wiley, NewYork, pp 217–249
Kitamura M, Yamashita K, Imai H (1976) Studies on the electrode processes of oxovanadium(IV). II. Electrolytic reduction of vanadyl acetylacetonate in acetonitrile solution at mercury electrode. Bull Chem Soc Jpn 49:97–100
Tsuchida E, Yamamoto K, Oyaizu K, Iwasaki N, Anson FC (1994) Electrochemical investigations of the complexes resulting from the acid-promoted deoxygenation and dimerization of (N, N′-ethylenebis(salicylideneaminato))oxovanadium(IV). Inorg Chem 33:1056–1063
Tsuchida E, Oyaizu K, Dewi EL, Imai T, Anson FC (1999) Catalysis of the electroreduction of O2 to H2O by vanadium–salen complexes in acidified dichloromethane. Inorg Chem 38: 3704–3708
Chatterjeea M, Ghosha S, Wub BM, Mak TCW (1998) A structural and electrochemical study of some oxovanadium(IV) heterochelate complexes. Polyhedron 17:1369–1374
Tasiopoulos AJ, Troganis AN, Evangelou A, Raptopoulou CP, Terzis A, Deligiannakis Y, Kabanos TA (1999) Synthetic analogues for oxovanadium(IV)–glutathione interaction: an EPR, synthetic and structural study of oxovanadium(IV) compounds with sulfhydryl-containing pseudopeptides and dipeptides. Chem Eur J 5:910–920
Tajika Y, Tsuge K, Sasaki Y (2005) Mononuclear oxovanadium complexes of tris(2-pyridylmethyl)amine. Dalton Trans 1438–1447
Asgedom G, Sreedhara A, Rao C, Kolehmainen E (1996) Monooxovanadium(V) mixed ligand complexes of Schiff bases and catecholates: synthesis, spectral and electrochemical characterization. Polyhedron 15:3731–3739
Nakajima K, Kojima K, Kojima M, Fujita J (1990) Preparation and characterization of optically active Schiff base-oxovanadium(IV) and -oxovanadium(V) complexes and catalytic properties of these complexes on asymmetric oxidation of sulfides into sulfoxides with organic hydroperoxides. Bull Chem Soc Jpn 63:2620–2630
Asgedom G, Sreedhara A, Rao C (1995) Oxovanadium(V) Schiff base complexes of trishydroxymethylaminomethane with salicylaldehyde and its derivatives: synthesis, characterization and redox reactivity. Polyhedron 14:1873–1879
Ghosh S, Nanda KK, Addison AW, Butcher RJ (2002) Mononuclear and mixed-valence binuclear oxovanadium complexes with benzimidazole-derived chelating agents. Inorg Chem 41: 2243–2249
Maurya MR, Kumar A, Abid M, Azam A (2006) Dioxovanadium(V) and μ-oxo bis[oxovanadium(V)] complexes containing thiosemicarbazone based ONS donor set and their antiamoebic activity. Inorg Chim Acta 359:2439–2447
Hirao T (1997) Vanadium in modern organic synthesis. Chem Rev 97:2707–2722
Bolm C, Bienewald F (1996) Asymmetric sulfide oxidation with vanadium catalysts and H2O2. Angew Chem Int Ed Engl 34:2640–2642
Takizawa S, Katayama T, Sasai H (2008) Dinuclear chiral vanadium catalysts for oxidative coupling of 2-naphthols via a dual activation mechanism. Chem Commun 35:4113–4122
Conte V, Floris B (2010) Vanadium catalyzed oxidation with hydrogen peroxide. Inorg Chim Acta 363:1935–1946
Pecoraro VL, Slebondnic C, Hamstra B (1998) Synthetic models for vanadium haloperoxidases. ACS symposium series, 711(Vanadium Compounds):157–167
Waidmann CR, DiPasquale AG, Mayer JM (2010) Synthesis and reactivity of oxo-peroxo-vanadium(V) bipyridine compounds. Inorg Chem 49:2383–2391
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2012 Springer Science+Business Media B.V.
About this chapter
Cite this chapter
Kanamori, K., Tsuge, K. (2012). Inorganic Chemistry of Vanadium. In: Michibata, H. (eds) Vanadium. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0913-3_1
Download citation
DOI: https://doi.org/10.1007/978-94-007-0913-3_1
Published:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-007-0912-6
Online ISBN: 978-94-007-0913-3
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)