Peroxido complexes of vanadium

Accepted Manuscript Title: Peroxido complexes of vanadium Author: Peter Schwendt Jozef Tatiersky Luk´asˇ Krivosudsk´y ˇ M´aria Simunekov´ a PII: DOI: Reference:

S0010-8545(15)30141-7 http://dx.doi.org/doi:10.1016/j.ccr.2016.03.011 CCR 112224

To appear in:

Coordination Chemistry Reviews

Received date: Revised date: Accepted date:

23-12-2015 16-3-2016 24-3-2016

Please cite this article as: P. Schwendt, J. Tatiersky, L. Krivosudsk´y, M. ˇ Simunekov´ a, Peroxido complexes of vanadium, Coordination Chemistry Reviews (2016), http://dx.doi.org/10.1016/j.ccr.2016.03.011 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

Peroxido complexes of vanadium Peter Schwendt, Jozef Tatiersky, Lukáš Krivosudský, Mária Šimuneková

Department of Inorganic Chemistry, Comenius University, Faculty of Natural Sciences,

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Mlynská dolina, Ilkovičova 6, 842 15 Bratislava, Slovakia

Abstract

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Peroxido complexes represent an important group of vanadium compounds having practical applications in distinct areas of chemistry. They possess insulin mimetic properties, antitumor

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activity and stimulate or inhibit certain enzymes. The bioinorganic chemistry of peroxidovanadates studies also the role of vanadium in the active centers of vanadium

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dependent enzymes (haloperoxidases and nitrogenases). Peroxidovanadium compounds are intensively studied for their oxidative properties. They can act as catalysts or stoichiometric oxidants in oxidation reactions of organic compounds, e.g. in epoxidation, sulfoxidation,

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hydroxylation or bromination. This versatility of vanadium peroxido complexes necessitates a critical review of their molecular structure and properties both in solution and in solid state. In

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this inclusive review we present the complete set of peroxido complexes of vanadium

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heretofore characterized by X-ray diffraction analysis. Along with the molecular structures we present and discuss the solid state vibrational spectra and thermal decomposition data. Vibrational, UV-vis and 51V NMR spectra of complexes dissolved in various solvents are also discussed. We have extracted the data from several speciation studies in order to clarify the formation conditions for different types of peroxidovanadates and summarize their 51V NMR chemical shifts. We also refer to certain applications of peroxido complexes of vanadium and we place the emphasis on potential applications which have not yet been thoroughly examined but deserve more attention.

Keywords: peroxido/peroxo complexes of vanadium; peroxidovanadates; molecular structure; vibrational spectra; 51V NMR spectra, thermal decomposition.

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Contents

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1 Introduction 2 Peroxidovanadium species in solution 3 Synthesis 4 Molecular structure 4.1 Tetraperoxido complexes 4.2 Triperoxido complexes 4.3 Diperoxido complexes 4.3.1 Mononuclear diperoxido complexes 4.3.2 Dinuclear diperoxido complexes 4.3.2.1 Symmetric structures 4.3.2.2 Asymmetric structures 4.3.3 Trinuclear diperoxido complexes 4.3.4 Tetranuclear diperoxido complexes 4.4 Triperoxido divanadates 4.5 Monoperoxido complexes 4.5.1 Mononuclear complexes 4.5.1.1 Hexacoordinated mononuclear complexes 4.5.1.2 Heptacoordinated mononuclear complexes 4.5.2 Dinuclear monoperoxido complexes 4.5.3 Polymeric monoperoxido complexes 4.6 Peroxido complexes with unusual structure 4.7 Concluding remarks and structural similarities with the active site of chloroperoxidase Curvularia inaequalis 5 Solid state vibrational spectra 6 Solid state 51V NMR spectra 7 Thermal decomposition 8 Solution properties 8.1 Vibrational spectra 8.2 Uv–vis spectra 8.3 51V NMR spectra and stability in solution 9 Outlook and perspectives Acknowledgements References

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1 Introduction Soon after discovery of vanadium (Sefström 1831) [1, 2, 3] the reaction between V2O5 and hydrogen peroxide was studied [4, 5]. On dissolution of V2O5 in diluted H2O2 a red solution is formed, which can serve as a sensitive qualitative proof of vanadium. First papers describing the synthesis of homoligand1 peroxidovanadium2 [6] complexes appeared by the end of the 19th century when Melikov and Pissarevski reported the

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preparation of several peroxidovanadates [7]. Later on, Beltrán-Martinez (1943–1956) and Jahr et al. (1934–1960) have prepared a series of homoligand peroxido complexes, e. g.

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M3[V(O2)4] and M4[V2O3(O2)4] [7]. The first heteroligand1 peroxido complex of vanadium, NH4[VO(O2)(dipic)(H2O)], was described by Hartkamp (1959) [8]. Twelve years later, the

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first crystal structure of peroxidovanadium complex, (NH4)4[V2O3(O2)4], was published by Svensson and Stomberg [9].

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The increasing attention in the last decades to the vanadium chemistry was evoked by important discoveries on the role of vanadium compounds in biological systems. The presence of vanadium in the active center of vanadium dependent enzymes (haloperoxidases and

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nitrogenases), the insuline mimetic properties and antitumor activity, and even the stimulation and inhibition of many enzymes by vanadium compounds became the main topics in

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bioinorganic vanadium chemistry. All these aspects of vanadium compounds have been in

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detail reported in a series of reviews [10] and books [11]. The peroxidovanadium compounds are closely related to at least three biological effects mentioned above. The crystal structure of vanadium chloroperoxidase from Curvularia inaequalis has shown that the active site of the peroxido form of the enzyme contains the V(η2-O22–) fragment [12] as a typical part of peroxidovanadium complexes. Structural and functional modelings of the active site of haloperoxidases are subject of many studies [13, 14]. Several vanadium peroxido complexes exhibit cytostatic effects [15], e. g. NH4[VO(O2)2(bpy)]·4H2O, NH4[VO(O2)2(phen)]·2H2O [16, 17] and K2[VO(O2)2(pic)] [18, 19]. Insuline-enhancing properties were observed for many peroxidovanadium compounds, e.g. [VO(O2)2(pic)]2– and [VO(O2)2(phen)]–. The latter complex is a potent protein phosphotyrosine phosphatase inhibitor lowering the blood glucose level even when transdermally delivered to experimental animals (mouse) [12, 18]. The wellknown inhibition of phosphatases by vanadate (VO43–) has stimulated the research on 1

In this review, the term „homoligand“ is used for peroxido complexes containing O2–, O22–, H2O and/or OH–; the term “heteroligand” is used for all other peroxido complexes. 2 According to IUPAC recommendations on the nomenclature of inorganic chemistry (IUPAC Red Book 2005), (O2)2– is the “peroxido” ligand, although in majority of papers still “peroxo” is used. The Scopus database search provided 155 results for “vanadium peroxo” or “peroxovanadates”, but only 20 for “peroxido” (in 2005 – 2014).

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vanadium complexes as phosphatase inhibitors [20], which is very relevant property of vanadate. Since the classical work published by Mimoun et al. [21], many results have been obtained in the field of oxidations of organic compounds under involvement of peroxidovanadium compounds as catalysts or stoichiometric oxidants. In these reactions, peroxidovanadium compounds are usually formed in situ from vanadium containing precursors, mostly

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ammonium or alkaline metal vanadates, resp. V2O5 and hydrogen peroxide or an alkyl hydrogen peroxide. Peroxidovanadium compounds are able to oxidize aliphatic and aromatic

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hydrocarbons, sulfides, alcohols etc. The reactivity of vanadium peroxido complexes in oxidation reactions was, in addition to the already mentioned books [11], the subject of a

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series of excellent reviews [22]. Recently, studies on catalytically active polymer anchored peroxidovanadium complexes have been reported [23, 24, 25].

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In this review we deal only with compounds with molecular structure unequivocally determined by X–ray analysis. We discuss the synthesis, molecular and crystal structures and vibrational spectra of solid complexes and their thermal decomposition as well as some

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solution properties of the complexes: vibrational, UV–vis and 51V NMR spectra, and stability in various solvents. We would like to present here a thorough and, to the best of our

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knowledge, a complete overview of crystallographically characterized peroxido complexes of

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vanadium with all n(O22–)/n(V) ratios known so far in mono-, di-, tri-, tetranuclear and polymeric solid state structures. This topic was already partially dealt in our previous publication on monoperoxidovanadates [26].

2 Peroxidovanadium species in solution

Most of heteroligand peroxidovanadium complexes can be derived from the homoligand complexes. Therefore, in this part we describe the speciation of homoligand complexes in aqueous and partially also in other solvents. The first consistent data on speciation were obtained by UV–vis spectroscopy and cryoscopy (extensive studies were performed by Chaveau [27,28]), but the most consistent data were later obtained using potentiometry and 51

V NMR spectroscopy. The formulation of species differs by various authors. In the

summarizing Table 1 we used, when possible, the formulae derived from molecular structures found for solid state homoligand and heteroligand peroxido vanadium complexes. When necessary, the formulae were completed by water molecule(s) to achieve the pentagonal pyramidal surroundings around the vanadium center. As can be seen from Table 1, the positions of the

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V NMR signals found by individual authors slightly differ due to the 4

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influence of ionic strength, temperature and vanadium concentration (cV), but the overall picture is similar. In aqueous solution, there were found 14 homoligand species with n(O22– )/n(V) ratios equal to 0.5, 1, 2, 3 and 4. The data in Table 1 were mainly taken from the papers by Howarth et al. [29, 30], Tracey et al. [31], and from the most thorough studies published by Pettersson et al. [32, 33, 34] In the cited references the reader can find also formation constants and distribution curves calculated for various experimental conditions. Other

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speciation studies published by Griffith et al. [35] and Conte et al. [36] have confirmed the general picture on composition of peroxido vanadium complexes in aqueous solutions.

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Table 1. 51V NMR signals for homoligand peroxidovanadium complexes. Tracey et al. [31] Pettersson et al. [32, Howarth et al. [29, 33] 30]a c(V) 0.01 – 2.0 mol/L 0.5 – 3.0 mmol/L 20 – 80 mmol/L n(H2O2) : n(V) mostly 2 1 – 10 1–5 pH 0 – 13 6 – 10 1 – 10 T 273 K ambient temp. 293 K ionic strength 2 mol/L NaClO4 1 mol/L KCl 0.15 mol/L NaCl Chemical shifts in ppm relative to VOCl3 Tetraperoxido complexes [V(O2)4]3− (purple) −737.6 Triperoxido complexes [V(O2)3(OH)]2− (yellow) −737.2, –733.2 −733 −732.2 Diperoxido complexes [VO(O2)2(OH)]2− (yellow) −770.6, –765.6 −765 −764.5 [VO(O2)2(H2O)]− (yellow) −699.9, –696 −686 −691.1 [V2O2(O2)4(OH)]3− −766.5, –757 −758 −754.5 [HVO(O2)2(H2O)]0 [V3O3(O2)6]3− Triperoxidodivanadates [V2O2(O2)3(H2O)2] −670.6 and −674.0 −669 Monoperoxido complexes [VO2(O2)(OH)(H2O)]2− −627.3 −625 −624.5 [VO(O2)(H2O)3]+ (red) −549, –543 −539.5 [VO(O2)(OH)2(H2O)]− −602 [V2O5(O2)2(H2O)2]4− −636.3 −633.6 [HO3VOVO(O2)2]3− −556.2 and −742.8 −554.9 and –737.0 - missing data a The chemical shifts in references [29] and [30] differ so we have included both values.

−702 [36] −710 [42]

It must be noted that nearly all speciation studies were performed for relatively low cV. The precise equilibrium studies require an adjustment of the ionic strength which is, however, in fact limiting the highest possible values of cV. Moreover, most of the investigations were aimed at the modeling of vanadium compounds in biological systems with naturally low cV. The physiological conditions (cNaCl = 0.150 mol/L) limit the maximum vanadium concentration to several tenths of mmol/L. The highest cV studied was mostly profoundly

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lower than cV during the crystallization of solid complexes. There is some indication that the situation in solutions with cV > 1 mol/L might be different [37]. There are also some data on formation and behavior of peroxido vanadium species in nonaqueous

solutions,

mainly in

CH3CN.

The assignment of chemical shifts for

peroxidovanadium species in non-aqueous solutions is important because most of the oxidations take place in organic solvents [38, 39, 40]. Slebodnick and Pecoraro studied the V NMR shifts of simple oxovanadate oligomers and peroxidovanadium species in mixed

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water/acetonitrile solvents. The chemical shifts for all assigned species move downfield as the

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water concentration decreases, but the magnitude of the shift difference strongly depends on the species. The most drammatic difference was observed for [VO(O2)(H2O)3]+: the

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corresponding signal moves from –539.9 (100 % H2O) to –449.9 ppm (2 % H2O / 98 % CH3CN) [41]. In concentrated aqueous solutions the trinuclear complex [V3O3(O2)6]3– is

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formed as a minor species, which becomes dominant in solutions with high acetonitrile content. Further speciation studies in the mixed water/acetonitrile solvents revealed that a higher concentration of acetonitrile supports the formation of oligomeric species, namely

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[V2O2(O2)4H2O]2− and [V3O3(O2)6]3− [42]. This was in good agreement with the work of Slebodnick and Pecoraro who predicted, based on their results, that acetonitrile stabilizes the

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higher oligomers of peroxidovanadates and vanadates. This crucial finding will allow better

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understanding of composition of reaction mixtures in catalytic systems. An interesting study of preferential solvation and complexation by various solvents was presented by Conte et al. [43] It demonstrates different behavior of solvents as far as the solvation and coordination to vanadium center is concerned. Thus, the [VO(O2)2(H2O)]– ion exhibits in CH3CN/H2O mixed solvent only one 51V NMR signal, while in CH3OH/H2O and DMF/H2O two different signals can be observed. Recent results [42] have shown that from the two possibilities suggested by Conte et al. [43], namely that no substitution of water by acetonitrile molecule is taking place or that such a process is very fast, the first alternative seems to be more probable. For CH3OH/H2O and DMF/H2O solvents, the entrance of CH3OH or DMF into the coordination sphere of vanadium can be expected. Similar substitution of coordinated H2O by solvent molecule we supposed for formamide/water solvent and different 51

V NMR signals for [VO(O2)2(H2O)]– and [VO(O2)2(HCONH2)]– were observed [44]. In

spite of these results, the non-aqueous solutions are insufficiently examined and deserve a further investigation.

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3 Synthesis The reaction systems for the preparation of vanadium(V) peroxido complexes are usually simple:

vanadium precursor – H2O2 – ligand/s – solvent / (cosolvent).

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Mostly, V2O5 or MVO3 (M = K, NH4 , Na) serve as source of vanadium. When using NR4VO3 (R = alkyl) as starting compound, this vanadate is usually prepared in situ from NR4OH and

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V2O5 or from NR4OH and NH4VO3 on subsequent boiling, without isolation of corresponding solid metavanadates. Sometimes, vanadium compounds with oxidation number of vanadium

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atoms different from five, e. g. VOSO4 [45] or VCl3 [46, 47, 48, 49], and very rarely heteroligand vanadium complexes have been used as starting compounds [14, 50, 51, 52].

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The ligands are added to the reaction system as solids or dissolved in appropriate solvent (water, ethanol, methanol, acetonitrile, THF, etc.). The required pH of the initial aqueous solution may comprise nearly the whole pH scale (0 – 14). It depends on the type of the

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complex intended and is achieved either by acidification (H2SO4, HClO4, HCl) or by adding bases (alkaline hydroxides, ammonia solution, NR4OH). Sometimes, the crystallization has to

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be initiated by addition of a cosolvent (ethanol, methanol, THF). Reactions, when the peroxido complexes are formed by interaction of vanadium compounds

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with molecular oxygen, deserve special attention. Because the transformation of O2 into O22− is a two-electron process, a mononuclear vanadium(III) complex would be particularly suitable for the reaction with O2: V(III) + O2 → V(V) + O22−. This route was used by Cozzolino et al. [53] for the synthesis of the unique peroxido vanadium complex without the typical V=O group:

[VIII(tbdma)3] + O2 → [VV(η2-O2)(tbdma)3]

When vanadium(IV) complex is used for the reaction with O2 some side processes must accompany the main reaction to ensure the electron balance. The mechanism of the oxidation of VIV to VVO(O2)+ is still under discussion [54], but it seems that the crucial role is played by solvent. Up to know the following reactions were described (refs: I [45], II [52], III, [55], IV [56], V [54], VI [57]):

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tert-butylalcohol

toluene

diethylether (THF)

[VIVO(L-N4Me2)(CH3CN)]2+ + O2 [VIVO(OH)(4,4’-tBu2bpy)2]+ + O2

[VVO2(L1)(L2)] + [VVO(O2)(L1)(L2)]

II

[VVO(O2)(tpa)]+

III

CH3CN, THF

[VVO(O2)(L-N4Me2)]+

CH3CN, THF

CH3OH

[VVO(O2)(4,4’-tBu2bpy)2]+

[{VVO(O2)}2(bpbp)]+

IV V VI

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[{VIVO(H2O)}2(bpbp)]3+ + O2

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[VIVO(OH)(H2O)(L1)] + L2 + O2 [VIVOCl(tpa)]+ + O2

[VVO(O2)(pan)(py)]

H2O, CHCl3

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VIVOSO4 + Hpan + py + O2

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4 Molecular structures Scheme 1 summarizes the coordination modes of the O22− ligand to vanadium center and the geometry of complexes. There is no proof of end-on-bonded peroxido ligand to vanadium atom from X–ray structure analysis. The typical coordination numbers of central vanadium atoms for complexes with n(O22−)/n(V) ≤ 2 are 6 (pentagonal pyramid) and 7 (pentagonal bipyramid). An important exception is the “Brégeault complex”, PPh4[VO2{Ph3SiO}2]x-

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[VO(O2){Ph3SiO}2]1−x (x = 0.57) [58], where in the peroxido fragment of the complex the coordination number of the vanadium atom is 5. Another curious example of a complex with

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a five-coordinate vanadium(V) center is the only “non-vanadyl” complex [V(η2-O2)(tbdma)3] [53]. There is some discussion on what is the distance between a vanadium center and atom in

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the trans position to the double bonded oxygen atom of the V=O group (d(V–Lax)) which should be taken into account when deciding the type of coordination polyhedron. We have

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chosen the distance ≈2.5 Å as arbitrary limit for this purpose, because up to this distance the occupation of the seventh position in coordination sphere exhibit an influence on vibrational spectra of diperoxido complexes (type b in Scheme 1) [59]. Such an arrangement with d(V–

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section 5 Solid state vibrational spectra.

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Lax) ≈ 2.5 Å was designated as pseudopentagonal bipyramidal [60]. For further discussion see

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Scheme 1. Coordination modes of the O22– ligand to the vanadium atom derived from the crystal structures of compounds listed in Table 2 and Scheme 2. L is donor atom of the heteroligand.

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4.1 Tetraperoxido complexes Blue tetraperoxidovanadates crystallize from strongly basic solutions containing high excess of hydrogen peroxide (n(H2O2)/n(V) >> 10). The [V(O2)4]3− anion possesses distorted dodecahedral structure with approximate D2d symmetry (compounds 1–4 in Table 2 and

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Scheme 2). Table 2. Structurally characterized peroxido complexes of vanadium(V).a,b

37 38 39 40

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References

dodecahedron dodecahedron dodecahedron dodecahedron

[61] [61] [62] [62]

b b b b b b b b b b b b b b b b b b b b b b b b b b b b b b b b

[63] [64] [65] [66] [67,68] [44] [69] [70] [71] [72] [73] [74] [75] [75, 76] [77] [78] [79] [79] [80] [81] [81] [82, 83] [83] [83] [83] [83] [84] [85] [85] [86] [86] [87]

f f f f

[88] [89] [90] [91]

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5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

Coord. mode

d

1 2 3 4

Compound n(O22–)/n(V) = 4 Na3[V(O2)4]·H2O2·10.5H2O Na3[V(O2)4]·14H2O (NH4)3[V(O2)4] K3[V(O2)4] n(O22–)/n(V) = 2 NH4[VO(O2)2(NH3)] K2[VO(O2)2F] Cs2[VO(O2)2F] (NH4)2[VO(O2)2F] (Him)[VO(O2)2(im)] (H2en) [VO(O2)2F] [Zn(NH3)4][VO(O2)2(NH3)]2 [Ni(NH3)6][VO(O2)2(NH3)]2 Na[VO(O2)2{(CH3)3NCH2CO2}]c Hmba[VO(O2)2(mba)]·H2O (NH4)3[VO(O2)2F2] K3[VO(O2)2(ox)]·H2O K3[VO(O2)2(ox)]·H2O2 NH4[VO(O2)2(bpy)]·4H2O Hbpy[VO(O2)2(bpy)]·(3+x)H2O2·(2–x)H2O K3[VO(O2)2(CO3)] K2[VO(O2)2(pic)]·2H2O K2[VO(O2)2(OHpic)]·3H2O K[VO(O2)2(5-nitro-1,10-phen)]·2H2O K3[VO(O2)2(2,4-pdc)]·3.25H2O K3[VO(O2)2(3-acetpic)]·2H2O Na[VO(O2)2(bpy)]·8H2O Li[VO(O2)2(bpy)]·5H2O K[VO(O2)2(bpy)]·4H2O Rb[VO(O2)2(bpy)]·4H2O Cs[VO(O2)2(bpy)]·4H2O NH4[VO(O2)2(py-im)]·4H2O NH4[VO(O2)2(pprd)]·2H2O NH4[VO(O2)2(2-NH2-pprd)]·3H2O Ca[VO(O2)2(NH2CH2COO)]·4H2O Sr[VO(O2)2(NH2CH2COO)]·4H2O NH4[VO(O2)2(pzpy)]·6H2O dinuclear (NH4)4[V2O3(O2)4] K4[V2O3(O2)4]·H2O K3(H3O)[V2O3(O2)4] K3[HV2O3(O2)4]·H2O

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No.

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59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94

11

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[92] [59] [93] [93] [94] [95] [96] [97] [98] [99] [71] [71] [100] [101]

h

[42]

4×b

[102]

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57 58

f 2×b 2×b 2×b 2×b g g g g g g g b b

M

56

d

55

(NH4)3[HV2O3(O2)4]·H2O (NH4)5[V2O2(O2)4(PO4)]·H2O (H3O)2[{VO(O2)2}2(Hgly)]·5/4H2O K2[{VO(O2)2}2(Hgly)]·H2O (H2en)2[V2O2(O2)4(µ-C2O4)] (NMe4)2[V2O2(O2)4(H2O)]·2H2O K2[V2O2(O2)4(H2O)]·3H2O (H2cym)[V2O2(O2)4(H2O)]·2H2O Cs3[V2O2(O2)4F]·H2O K3[V2O2(O2)4(IO3)]·H2O K2[V2O2(O2)4{(CH3)3NCH2CO2}]·H2O (NH4)2[V2O2(O2)4{(CH3)3NCH2CO2}]·0.75H2O Hbpy[H{VO(O2)2(bpy)}2]·xH2O2·(6–x)H2O NBu4{[VO(HO2)(O2)(phen)][VO(O2)2(phen)]} trinuclear (NBu4)3[V3O3(O2)6]·2H2O tetranuclear K7[V4O4(O2)8(PO4)]·9H2O n(O22–)/n(V) = 3/2 K3[V2O2(O2)3F3]·2H2O·HF Cs3[V2O2(O2)3F3]·H2O·2HF n(O22–)/n(V) = 1/1 (NEt4)[VO(O2)(glygly)]·1.58H2O [VO(O2)(pic)(H2O)2] [VO(O2)(phen)](H2O)2]Cl·0.38H2O [VO(O2)(pic)(pcaa)(H2O)]·H2O K3[VO(O2)(ox)2]·0.5H2O [VO(O2)(pic)(bpy)]·H2O [VO(O2)(bpy)2]ClO4 [VO(O2)(phen)2]ClO4 PPh4[VO(O2)(pic)2]·2.5H2O [VO(O2)(pic)(phen)]·0.5CH2Cl2 NH4[VO(O2)(pca)2]·2H2O (H3tren)[VO(O2)(ox)2]·3H2O K[VO(O2)(ox)(bpy)]·3H2O NPr4[VO(O2)(ox)(phen)] [VO(O2)(pa)2]ClO4·3H2O [VO(O2)(pca)(pa)]·H2O NH4[VO(O2)(3OH-pic)2]·H2O (H2en)[VO(O2)(ox)(pic)]·2H2O (H2en)[VO(O2)(ox)(pca)] [VO(O2)(pca)(bpy)] [VO(O2)(pca)(phen)] [VO(O2)(pic)(pa)]·H2O [VO(O2)(Hquin)(pa)]·2H2O [VO(O2)(4,4-Me2bpy)2][BF4] [VO(O2)(pan)(phen)] [Fe(bpy)3][VO(O2)(ox)(bpy)]2·7H2O [Ni(bpy)3][VO(O2)(ox)(bpy)]2·7H2O NH4[VO(O2)(dipic)(H2O)]·xH2O (x ≈ 1.3) NH4[VO(O2)(dipic)(H2O)] [VO(O2)(pan)(py)] [VO(O2)(TpPri2)(HPzPri2)]·THF [VO(O2)(Hsalhyhb)(H2O)]·H2O [VO(O2)(pzH)(HB(pz)3] (H3O)[VO(O2)(dipic)(H2O)]·1.5H2O [VO(O2)(aptch)(CH3OH)] (Hpa)[VO(O2)(dipic)(H2O)]·H2O

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41 42 43 44 45 46 47 48 49 50 51 52 53 54

i i

[103,104] [98]

a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a a

[105] [21] [51,50] [106] [107] [108] [109,110] [109, 110] [50,51] [50,51] [111] [112] [113] [113] [114] [114] [115] [116] [116] [106] [106] [117] [117] [54] [118] [119] [119] [120] [121] [45] [52] [122] [123] [124] [125] [126]

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a a a a a

100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126

(NH4)2[VO(O2)(Hedta)]·4H2O K2[VO(O2)(Hedta)]·4H2O Ba[VO(O2)(nta)]·3H2O K[VO(O2)(Hheida)]·H2O K2[VO(O2)(nta)] Na2[VO(O2)(nta)]·5H2O K[VO(O2)(ada)]·4H2O [VO(O2)(bpg)]·H2Od Cs[VO(O2)(ceidaa)]·H2O K[VO(O2)(ceidaa)]·2H2O K[VO(O2)(DL-cmhist)]·H2O [VO(O2)(Hbpa)]ClO4·2H2O [VO(O2)(L-N4Me2)][BPh4] K3[VO(O2)(2,5-pdc)]·4.5H2O K[VO(O2)(NH2pyg2)]·2H2O K[VO(O2)(BrNH2pyg2)]·H2O K[VO(O2)(omeida)]·H2O K[VO(O2)(Hheida)]·2H2O [VO(O2)(tpa)]Cl·0.5CH3OH·1.5H2O [VO(O2)(modbndc)]ClO4·H2O PPh4[VO(O2)(sbtbph)]·C6H14 [VO(O2)(imala)]·2H2O Na[VO(O2)(edda)]·H2O K2[VO(O2)(ceida)]·H2O Cs2[VO(O2)(Hedds)]·3.5H2O [VO(O2)(bimgly)]·2H2O [VO(O2)(Hbpa)]2(ClO4)2·[VO(O2)(bpa)]·2.25H2O dinuclear (NH4)2[{VO(O2)(DL-Hmal)}2]·2H2O K2[{VO(O2)(L-H2tart)}2(µ-H2O)]·5H2O (NBu4)2[V2O2(O2)2(glyc)2]·H2O (NBu4)2[V2O2(O2)2(DL-mand)2]· DL-H2mand K2[{VO(O2)(lact)}2] (NBu4)2[V2O2(O2)2(L-lact)2]·2H2O (NBu4)2[V2O2(O2)2(D-lact)( L-lact)]·2H2O K4[{VO(O2)(mal)}2]·H2O (NH4)4[{VO(O2)(mal)}2]·3H2O K2[{VO(O2)(Hmal)}2]·2H2O (NMe4)2[V2O2(O2)2(R,S-mand)2]·6.5H2O (NMe4)(NH4)[V2O2(O2)2(R,S-mand)2(H2O)]·2H2O (NEt4)2[V2O2(O2)2(R-mand)2] (NBu4)2[V2O2(O2)2(R-α-hhip)(S-α-hhip)]·5H2O (NPr4)2[V2O2(O2)2(R-α-hhip)(S-α-hhip)]·5H2O (NH4)6[{VO(O2)(cit)}2]·4.5H2O (NH4)2[{VO(O2)(H2cit)}2]·2H2O K2[{VO(O2)(H2cit)}2]·2H2O (NEt4)(NH4)3[V2O2(O2)2(R-3-phlact)2][V2O2(O2)2(S-3-phlact)2]·6H2O K10[V2O2(O2)2(Hcit )2] [V2O2(O2)2(cit)2]·20H2O (Hgdn)4[V2O2(O2)2(Hcit)2]·6H2O (NH4)6[V2O2(O2)2(H2cit)2] [V2O2(O2)2(Hcit)2]·6H2O (NH4)4[V2O2(O2)2((2R,3R)-H2tart)2(µ-H2O)][V2O2(O2)2((2S,3S)H2tart)2(µ-H2O)]· 8H2O

a a a a a a a a a a a a a a a a a a a a a a a a a a a

us

an

M

d

Ac ce pt e

127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149

12

c c c c c c c c c c c c c c c c c c c c c c c

[126] [126] [127] [164] [128,129, 130] [131] [132] [133] [134] [135] [136] [137] [14] [138] [139] [140,128] [141] [56] [142] [143] [143] [144] [115] [55] [145] [146] [147] [15] [15] [15] [15] [115]

ip t

(Hnica)[VO(O2)(dipic)(H2O)]·H2O (Hphen)[VO(O2)(dipic)(H2O)]·H2O [VO(O2)(pan)(CH3OH)] [VO(O2)(bzpy-inh)(H2O)]·0.5CH3OH K2[VO(O2)(nta)]·2H2O

cr

95 96 97 98 99

[148] [149] [150] [151] [152] [153] [153] [46] [46] [46] [154] [154] [154] [155] [156] [47] [157] [158] [159] [160] [161] [48] [162]

Page 12 of 46

152

[{VO(O2)}2(bpbp)]ClO4·H2O

153 154 155

157

[V2O2(O2)2(bzpy-tch)2] [Zn(H2O)6][V2O2(O2)2(glyc)]·2H2O (H2en)[V2O2(O2)2(glyc)]·4H2O polynuclear NH4[VO(O2)(ida)] others PPh4[VO2(Ph3SiO)2]x[VO(O2)(Ph3SiO)2]1–x (x = 0.57)

158

(NH4)4[(VO2){VO(O2)}(Hcit)2]·1.5H2O

159

[V(O2)(tbdma)3]

156

a special of d special of d e c c

type

[14] [163]

type

[57]

a

[164] [165] [165] [166]

ip t

[{VO(O2)}2{H(bpg)2}]ClO4·CH3CH2CN·CH3CN Cs3[V2O2(O2)2(dpot)]6H2O

quasi trigonal pyramidal a and non peroxido quasi trigonal pyramidal quasi a special type special type special type

cr

150 151

[58]

[49]

[53]

Ac ce pt e

d

M

an

us

[167] 160 [VO(O2-t-Bu)(dipic)(H2O)] [69] 161 [{VO(O2)2(NH3)}2{µ-Cu(NH3)4}] [168] 162 [Cd(NH3)6][{VO(O2)2(OH)}2(µ-Cd(NH3)4}] [168] 163 [{VO(O2)2(im)}2{µ-Cu(im)4}] a Structural formulae for ligands are given in Scheme 2. b We did not include data on [VO(O2)(bpz*eaT)·(VO)(C4H4O6)]·H2O [169] into Table 2, because we consider the coexistence of vanadium(IV) center and peroxido ligand in the same complex as improbable. Possible genuine formula is: [VVO(O2)(bpz*eaT)]+2[VV2O2(C4H2O6)2]2–·2H2O. See also the structure of the anion in ref. [170]. c This compound is formulated as polymer, where [VO(O2)2{(CH3)3NCH2CO2)}]– fragments are linked by NaOx polyhedra, but the vanadium complex is in principle mononuclear. d See also ref. [177].

13

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Ac ce pt e

d

M

an

us

cr

ip t

Scheme 2. Structural formulae of characterized peroxido complexes of vanadium(V)

14

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15

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cr

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16

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Ac ce pt e us

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cr

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17

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Ac ce pt e us

an

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cr

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18

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Ac ce pt e us

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cr

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19

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Ac ce pt e us

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cr

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20

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Ac ce pt e us

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cr

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Ac ce pt e us

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cr

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4.2 Triperoxido complexes There is a general agreement that the triperoxidovanadate [V(OH)(O2)3]2− is formed in neutral and basic solutions containing an excess of hydrogen peroxide and the corresponding solutions are reported to be pale yellow [30, 61]. For the mononuclear triperoxido complexes the [VL(O2)3]n− composition (L = monodentate ligand) and a capped trigonal prismatic structure can be supposed. Unfortunately, both published structures of triperoxido complexes

ip t

are reported unsatisfactorily. Only a short conference abstract was published concerning the structure of (NMe4)2[V(OH)(O2)3]·H2O [171], the full structure data were not reported later.

cr

The structure of (NH4)2[VF(O2)3]·H2O was refined only to 25% [172]. Moreover, this compound was reported to be blue and several attempts to reproduce the synthesis of

us

triperoxido complexes were unsuccessful3 [61]. Thus there is no unambiguously structurally

an

characterized triperoxido vanadium complex known so far.

4.3 Diperoxido complexes 4.3.1 Mononuclear diperoxido complexes

M

The central VO(O2)2 fragment in the coordination polyhedron of mononuclear diperoxido complexes has one or two vacant positions. These positions can be occupied by one

d

monodentate ligand (pentagonal pyramidal arrangement, 5–14 [44, 63, 64, 65, 66, 67, 68, 69,

Ac ce pt e

70, 71, 72]), two monodentate ligands (pentagonal bipyramidal geometry, 15 [73]) or one bidentate ligand (pentagonal bipyramidal structure, 16–36 [74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87]).

4.3.2 Dinuclear diperoxido complexes 4.3.2.1 Symmetric structures

Homoligand [{VO(O2)2}2(µ-O)]4− and [{VO(O2)2}2(µ-OH)]3− ions (37–41) [88, 89, 90, 91, 92] and heteroligand complexes with µ-PO43− (42) [59], µ-Hgly (43–44) [93] and µ-C2O42− (ox) (45) [94] ligands belong to this group. In all these structures, two VO(O2)2 fragments are symmetrically bound by bridging groups.

4.3.2.2 Asymmetric structures Quite surprisingly, there is a number of dinuclear diperoxido vanadium complexes where the coordination spheres of both vanadium centers are different. In these complexes the two 3

Our attempts to prepare (NH4)2[VF(O2)3]·aq resulted in products of different composition, which did not contain fluorine.

22

Page 22 of 46

VO(O2)2 fragments are connected by bridging peroxido oxygen atom bonded in a µ-η2:η1 mode. The additional ligand, i.e. H2O (46–48) [95, 96, 97], F− (49) [98], IO3− (50) [99], (CH3)3N+CH2CO2− (zwitterion, 51–52) [71] is bound only to one vanadium atom. The

dinucleating

role

of

a

strong

hydrogen

Hbpy[H{VO(O2)2(bpy)2]·xH2O·(6−x)H2O

bond

(53)

was

observed

[100]

(NBu4){[VO(HO2)(O2)(phen)][VO(O2)2(phen)]·3H2O2·H2O

(54)

in and

[101].

The

ip t

diperoxidovanadium fragments are bonded via strong O22–···H–O2– or O22–···H+···O22–

cr

hydrogen bond.

4.3.3 Trinuclear diperoxido complexes

us

The crystal structure of the elusive trinuclear cyclic anion [V3O3(O2)6]3− (55) [42] has been reported very recently (2015). The trinuclear species is composed of three VO(O2)2 fragments

an

connected by two µ-η2:η1 and one so far unobserved µ 3-η2:η1:η1 peroxido bridges. The

4.3.4 Tetranuclear diperoxido complexes

M

[V3O3(O2)6]3− anion is chiral and the reported crystal structure was a racemic compound.

There is only one tetranuclear vanadium diperoxido complex K7[V4O4(O2)8(PO4)]·9H2O (56) The

structure

of

the

tetranuclear

anion

resembles

the

structure

of

d

[102].

Ac ce pt e

(NH4)5[V2O2(O2)4(PO4)] (42) [59] but the PO43− ligand is bound to four vanadium centers instead of two.

4.4 Triperoxidodivanadates

Symmetric structure of the [V2O2(O2)3F3]3− ion consist of two VO(O2)F fragments which are connected by µ-η2:η2 peroxido ligands and a bridging fluorido ligand (57–58) [98, 103, 104]. This ion resembles the [V2O2(O2)3(H2O)x]0 species which was found in acidic aqueous solutions (Table 1) [32] and in which a similar symmetric structure can be expected.

4.5 Monoperoxido complexes 4.5.1 Mononuclear complexes The central VO(O2) fragment in mononuclear monoperoxido vanadium complexes leaves three or four positions vacant in the coordination polyhedron.

4.5.1.1 Hexacoordinated mononuclear complexes

23

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There is only one complex of this type: (NEt4)[VO(O2)(glygly)]·1.58H2O (59) [105]. The glygly ligand is acting as tridentate ligand with a NNO donor set.

4.5.1.2 Heptacoordinated mononuclear complexes The four remaining vacant positions of the pentagonal bipyramid can be occupied by bidentate + two monodentate (60–62) [21, 50, 51, 106], two bidentate (63–85) [50, 51, 54,

ip t

106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119], tridentate + monodentate (86–98) [45, 52, 121, 122, 123, 124, 125, 126, 127, 164] or tetradentate (99–

cr

126) [14, 15, 55, 56, 115, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147]

us

heteroligands.

4.5.2 Dinuclear monoperoxido complexes

an

There is a number of dinuclear monoperoxido complexes with anions of biologically important α-hydroxycarboxylic acids as heteroligands (127–149, 154–155) [46, 47, 48, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162], [165]. In these

M

complexes oxido and η2-peroxido ligands are coordinated to each of the two vanadium atoms, which are bridged by two oxygen atoms (µ-O)2, originating from the two deprotonated α-

d

hydroxy groups. The coordination number of the vanadium atoms is six (pentagonal

Ac ce pt e

pyramidal geometry) or seven (pentagonal bipyramidal arrangement). The central V2O4 fragment can adopt two different structures: anti (planar or nearly planar V2O2 core) or syn (non-planar V2O2 core) (Scheme 3). The formation of dinuclear α-hydroxycarboxylato monoperoxido vanadium complexes appears to be stereospecific: if the dinuclear anion contains achiral ligands or combination of R + S chiral ligands (achiral or racemic αhydroxycarboxylato ligand used in synthesis) then the orientation of the oxygen atoms of the V=O groups in the V2O4 fragment is anti. In the case of (R + R)/(S + S) combinations of enantiomerically pure α-hydroxycarboxylato ligands the oxygen atoms of the V=O groups in the V2O4 fragment adopt syn orientation4.

In [{VO(O2)}2{H(bpg)2}]ClO4·CH3CH2CN·CH3CN (150) [14], the two VO(O2)(bpg) fragments are connected through a hydrogen bond (one proton per dimer) similarly to the hydrogen bond in 53 [100]. The dinuclear structure of [V2O2(O2)2(dpot)]3– (151) [163] is composed of two VO(O2) fragments bridged by an alkoxo group of dpot5–. The bridging phenolato group of bpbp– links two monoperoxido VO(O2) fragments in 152 [57]. In

4

The only exception from this rule is K2[{VO(O2)(rac-lact)}2 (ref. [152]).

24

Page 24 of 46

[V2O2(O2)2(bzpy-tch)2] (153) [164], the bridging role is played by two µ-η1:η2 peroxido ligands.

Scheme 3. Syn and anti orientation of the oxygen atoms of the V=O groups in the V2O4 fragment in dinuclear

us

cr

ip t

monoperoxido complexes.

4.5.3 Polymeric monoperoxido complexes

The only polymeric peroxido vanadium complex is NH4[VO(O2)(ida)] (156) [166]. The

an

structure is composed of [VO(O2)(ida)]– polyhedra connected by relatively weak interionic

M

V···O bonds (2.375(3) Å) under formation of a polymeric chain.

4.6 Peroxido complexes with unusual structure

In the mixed crystals containing both the dioxido and oxidomonoperoxido complex

d

PPh4[VO2(Ph3SiO)2]x[[VO(O2)(Ph3SiO)2]1–x (x = 0.57) (157) [58], the monoperoxido part

Ac ce pt e

possesses pentacoordinated vanadium center with a trapezoidal pyramidal environment. Interestingly, such a pentacoordinated vanadium atom was found in the active site of vanadium haloperoxidases [12].

A

peroxido

vanadium

complex

with

n(O22–)/n(V)

=

0.5,

(NH4)4[(VO2){VO(O2)}(Hcit)2]·1.5H2O (158) [49] was prepared. This unique dinuclear complex is the first example with dioxido vanadium and oxido-peroxido vanadium fragments merged into one dinuclear anion.

The only monoperoxido complex without the terminal V=O group, [V(η2-O2)(tbdma)3] (159) [53], was obtained by aerial oxidation of the vanadium(III) complex [V(tbdma)3] (Section 3). The complex [VO(O2-tBu)(dipic)(H2O)] (160) [167] reported more than 30 years ago remains the one and only alkylperoxido complex known so far. The pentagonal bipyramidal structure of the complex is similar to other mononuclear monoperoxido complexes. There are also known three examples of compounds, where the diperoxido complex behaves as ligand coordinated to the other metal center, thus forming heterometallic compounds (161–

25

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163) [69, 168]. Interestingly, the diperoxido complex is coordinated in three different ways: via equatorial peroxido oxygen atom (161) [69], via equatorial OH– ligand (162) [168], and via doubly bonded oxygen atom (163) [168].

4.7 Concluding remarks and structural similarities with the active site of chloroperoxidase Curvularia inaequalis in

coordination

polyhedra of monoperoxido- and

cr

diperoxidovanadium complexes (Scheme 4) are summarized in Table 3.

ip t

Average interatomic distances

V=O

V–Op1

V–Op2

Op1–Op2

O

1.597

1.870

1.868

1.411

N

—

—

—

—

V–(E1)

V–(E2)

V–(E3)

V–(A)

2.180

Op1–Op2

—

—

V–(E)

V–(A)

1.466

—

—

2.026

2.448

—

—

—

—

2.138

2.309

—

—

—

—

1.908

2.406

2.029

2.014

2.030

2.245

2.150

2.148

2.283

Diperoxido complex V–Op1

V–Op2

O

1.610

1.900

1.883

N

—

—

F

—

—

Ac ce pt e

d

V=O

M

Donor atom in E and A

Monoperoxido complex

an

Donor atom in E1, E2, E3 and A

us

Table 3. Typical (average) interatomic distances in peroxido vanadium complexes (in Å). See also Scheme 4.

Scheme 4 Coordination polyhedra of monoperoxido- and diperoxidovanadium complexes.

O

O

Op2

Op1

V

Op2

E1

Op1

E2

E3

V

Op1

E

A

A

a

b

26

Op2

Page 26 of 46

Fig. 1. The schematic view of the active site of the peroxido form of a chloroperoxidase as determined by XRD analysis.

Monoperoxido complexes of vanadium are structurally similar to the active site of the peroxido form of chloroperoxidase secreted by the fungus Curvularia inaequalis (Fig. 1) [12]. The crystal structure of the enzyme was determined to the resolution 2.24 Å (R = 17.7 %). The vanadium atom is surrounded only by five direct donor atoms: two oxygen atoms O1 and

ip t

O2, one peroxido ligand O3O4 and one nitrogen donor atom N1 originating from imidazole ring of histidine. The bond length V–O1 ≈ 1.60 Å is similar to the bond length of the V=O

cr

group in both monoperoxido and diperoxido complexes. The bond lengths V–O3 and V–O4 ≈ 1.87 Å are very close to the mean value found for all structurally characterized monoperoxido

us

vanadium complexes. The remaining bond lengths are V–O2 ≈ 1.93 Å and V–N1 ≈ 2.19 Å. The empty coordination site in the apical position is proposed to be the accepting pocket for

an

chloride ion.

M

5 Solid state vibrational spectra

The characteristic groups in peroxidovanadium complexes, V(O2) (for tetraperoxido complex), VO(O2) and VO(O2)2 exhibit in vibrational spectra typical combinations of bands

d

(Table 1S). There are some significant differences between the spectra of monoperoxido and

Ac ce pt e

diperoxido complexes which are the most numerous groups of reviewed complexes. For monoperoxido complexes the bands corresponding to the Op–Op stretchings are always above 900 cm–1, while for diperoxido complexes these bands are below 900 cm–1. This difference is in accordance with the differences in the bond lengths (the Op–Op bond lengths are generally shorter in monoperoxido complexes – Table 3). In the region of V–Op stretching vibrations, the monoperoxido complexes exhibit typically two bands at about 560 cm–1, whereas vibrational coupling between two V(O2) groups in diperoxido complexes leads to a wider spectral range of these vibrations (649 – 446 cm–1). The spectra of diperoxido complexes usually contain four bands which can be assigned to the V–Op stretching vibrations (ν1, ν2, ν3 and ν4, Fig. 2)5. The wavenumber difference between ν1 and ν2 as well as the position of the band corresponding to ν3 vibration can be correlated with the coordination number of the vanadium center. When the d(V–L ) distance decreases (Scheme 1b) i) the ν~ (VO ) – ax

1

p

The number of bands corresponding to the ν(V–Op) vibrations can increase due to correlation effects in the unit cell. Because of the asymmetry of the V(O2) group, the distinguishing of asymmetric and symmetric vibrations of this group is incorrect. 5

27

Page 27 of 46

ν~2 (VOp) difference increases, and ii) the very strong Raman band corresponding to ν3(VOp) is shifted to lower wavenumbers (ν~3 (VOp) ≈ 530 cm–1 for pentagonal pyramidal geometry,

ν~3 (VOp) ≈ 480 cm–1 for pentagonal bipyramidal structure) [59, 93, 173]. The two rules are valid for d(V–Lax) below 2.5 Å. The characteristic spectral features are preserved also in the case when the VO(O2) and

ip t

VO(O2)2 groups are parts of oligomeric structures. The assignment of bands was supported by calculations using the classical GF methods [173, 174] or the more advanced DFT quantum chemical methods [72, 165]. These calculations point to some coupling of vibrations, but the

Ac ce pt e

d

M

an

us

cr

ν(V=O), ν(Op–Op) and ν(V–Op) stretchings are mostly sufficiently characteristic.

Fig. 2. IR in nujol mull (upper) and Raman (lower) spectra of K3[VO(O2)2(CO3)] (20) according to refs. [175, 176].

28

Page 28 of 46

6 Solid state 51V NMR spectra There are few data on solid state 51V MAS NMR spectra (Table 4). While for compounds 86 and 108 chemical shifts occurred in the expected region, the value for compound 13 is shifted from the diperoxido region (from –690 to –749 ppm in aqueous solution, Table 7) to the region typical for monoperoxido complexes in aqueous solution. Solid state

51

V MAS NMR

Table 4. Solid state 51V MAS NMR spectra. No. Compound Na[VO(O2)2{(CH3)3NCH2CO2}]·2H2O 13 NH4[VO(O2)(dipic)(H2O)]·xH2O (x = 1.3) 86 [VO(O2)(bpg)]·2H2Oa

Ref. [71] [178] [Error! Bookmark not defined.]

us

d

M

an

The structure of the complex is the same as in 107.

Ac ce pt e

a

Chemical shift [ppm] –558 –564.8 ± 3 –582 ± 1

cr

[177].

ip t

spectra were used for study of co-crystallized mixtures of [VO(O2)(bpg)] and [VO2(bpg)]

29

Page 29 of 46

7 Thermal decomposition Peroxido complexes of transition metals are of interest as molecular precursors for the preparation of oxide materials and oxometalates by decomposition reactions on heating [179, 180, 181]. For this purpose, the identification of products of thermal decomposition based just on the weight loss is insufficient. The intermediate and final products must be thoroughly characterized by several methods (X-ray powder diffraction, vibrational spectra, SEM, TEM

ip t

etc.). By this procedure, mainly oxide materials of Ti but also Mo, W, Nb, Ta, Ni, Fe, Co and Cu, and bimetallic Fe/Cu, Zr/Ti, Nb/Mo materials were prepared [182, 183, 184, 185, 186].

cr

The decomposition products of peroxidovanadium complexes were investigated in a number of studies [69, 70, 97, 98, 103, 137, 138, 139, 155, 187, 188, 189, 190, 191, 192, 193, 194,

us

195, 196, 197]. The decomposition of complexes proceeds in several steps. In the first step, the molecules of water, if present in the structure, are released. This endothermic process is followed by release of oxygen from the peroxido ligands, manifesting itself on the DTA curve

an

by a strong exothermic peak. The further decomposition depends on the heteroligands and counter ions. In the presence of simple heteroligands e.g. F–, CO32–, IO3–, C2O42–, the

M

decompositions result in formation of a mixture of vanadates with heteroligand containing compounds. The combustion of organic part of the compounds proceeds usually above 200 ºC and is accompanied by strong exotherms on the DTA curve. Typical DTA and TG curves are

Ac ce pt e

summarized in Table 5.

d

shown in Fig. 3. Reliably characterized decomposition products (up to 620 ºC) are

An interesting phenomenon is the reaction of decomposition intermediates, which are evidently coordinatively unsaturated, with the surrounding atmosphere. Thus, the decomposition intermediates of K4[V2O3(O2)4]·H2O and K3[V2O2(OH)(O2)4]·H2O react with carbon dioxide from air under formation of the carbonato complex (K3[VO(O2)2(CO3)]) [190]. The starting peroxidovanadates do not react with CO2 below the decomposition temperature.

Table 5. Products of thermal decomposition of peroxidovanadium complexes. No.

Formula

11

[Zn(NH3)4][VO(O2)2(NH3)]2

12

[Ni(NH3)6][VO(O2)2(NH3)]2

37

(NH4)4[V2O3(O2)4]

37

(NH4)4[V2O3(O2)4]

Intermediate decomposition product (t, °C) —

— NH4[VO(O2)2(NH3)] (60), NH4VO3 (125) NH4[VO(O2)2(NH3)]

30

Final decomposition product (t, °C) Zn(VO3)2 (550), monoclinic Ni2V2O7 + V 2O 5 V2O5 (150) NH4VO3 (145)

Atmosphere and methods of identification air, IR, XPD*

Ref.

[69]

air, IR, XPD

[70]

He, IR, TG/MS

[187]

N2, IR

[197]

Page 30 of 46

(93) 49

Cs3[V2O2(O2)4F]·H2O

—

58

Cs3[V2O2(O2)3F3]·H2O·2HF

—

161

[{VO(O2)2(NH3)}2{µ-Cu(NH3)4}]

V2O5, β-Cu2V2O7 (450)

CsF + CsVO3 (450) CsVO3 + Cs3[V2O4F5] Cu(VO3)2 (620), triclinic

air, IR, XPD

[98]

air, IR, XPD

[98]

air, IR, XPD

[69]

an

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cr

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* XPD – X-ray powder diffraction

Fig. 3. TG and DTA curves of thermal decomposition of [{VO(O2)2(NH3)}2{µ-Cu(NH3)4}] (161). According to

M

ref. [69].

d

It is probable that the character of intermolecular (interionic) forces is decisive for the stability of complexes in the solid state. The stability of molecules and ions themselves can

Ac ce pt e

also play some role (see e.g. the high solid state stability of K2[VO(O2)(nta)]·2H2O [193]). Generally, there are not enough data for conclusion about the factors which determine the stability of compounds in the solid state.

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8 Solution properties

8.1 Vibrational spectra Although vibrational spectroscopy, particularly the Raman spectroscopy, is an efficient tool for study of aqueous solutions, spectral studies of dissolved peroxido complexes are scarce. The analogy between solution and solid state spectra is a strong indication for the similarity of

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both the solid state and solution structures. There are two essential conditions for application of vibrational spectra for structural studies of solution species:

The complex under study must be the strongly dominant one in the solution.

ii.

The complex must be sufficiently soluble as the measuring of the vibrational spectra

cr

i.

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necessitates relatively high concentrations.

an

Selected data on solution vibrational spectra are summarized in Table 6.

IR 982 m

[VO(O2)2(H2O)]–

R 985

IR

894 s

984 s

888 s

949 vs

894 s

Ac ce pt e

992 vs

R 890

d

[VO(O2)(H2O)3]+

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Table 6. Selected data on solution vibrational spectra (cm–1). Solvent: H2O (D2O), other solvents: as indicated by note. Compound/complex ν(V=O) ν(OP–OP) ν(V–OP) Ref./note IR

NH4[VO(O2)2(NH3)] (5)

K3[VO(O2)2(ox)]·H2O (16)

(NBu4)3[V3O3(O2)6]·2H2O (55)

983 vs 965 vs

883 vs

963 s

R 632 535 476 634 m 538 vs 508 w 627 m 537 vs 496 sh 636 w 592 m 489 vs 472 sh

650 m 625 w 603 s 592 sh

951 vs

927 s

929 vs (D2O)

[198]

[199] 15 % NH3(aq) [198]

[42] CD3CN

[54] CH2Cl2

[VO(O2)(4,4-Me2bpy)2][BF4] (82) K2[VO(O2)(nta)]·2H2O (99)

[35]

570 m (D2O)

[193]

8.2 UV–vis spectroscopy Diperoxidovanadium complexes are mostly yellow and their aqueous solutions exhibit in UV–vis spectrum a characteristic band at ≈330 nm (Table 8).

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The UV–vis spectra of red (orange-red) monoperoxido complexes of vanadium in aqueous solution contain the characteristic band at ≈425 nm which corresponds to the combination of charge-transfer O22– → V and other (e. g. interligand [106]) transitions. For other solvents, the band is shifted to higher wavelengths, up to 500 nm (Table 7). 8.3 51V NMR spectra and stability in solution 51

V NMR spectroscopy is the most powerful method for investigation of

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The

peroxidovanadium complexes in solution. The sensitivity of the method is high; the detection

cr

limit for a vanadium species can be as low as 5 – 100 µmol/L [200]. In time when the

51

V

NMR spectroscopy was not at disposal, the speciation of vanadium peroxido complexes was

us

difficult or even impossible. The main problem was the decomposition of complexes in solution. Some data on UV–vis spectra were assigned to species not present in solution due to

an

decomposition of the original complex as was shown later on by 51V NMR spectroscopy. Table 7 summarizes chemical shifts of peroxido complexes of vanadium in various solvents, predominantly H2O/D2O. The signals of species in organic solvents are shifted downfield in

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comparison with the signals measured for aqueous solutions. The chemical shifts are slightly dependent also on temperature, c(V) and ionic strength. We included in Table 7 the data for

d

complexes forming only one vanadium species (i.e. there is only one signal in the 51V NMR

Ac ce pt e

spectrum) or complexes which are strongly dominant in solution. The Table 7 contains also data from studies in which the overall speciation was cleared by further experiments (e.g. ligand concentration study).

There is only a limited number of diperoxidovanadium complexes, for which the assignment of the 51V NMR shifts can be considered as reliable. The majority of complexes decompose in aqueous solutions on release of the heteroligand under formation of the [VO(O2)2(H2O)]– species (δ ≈ –690 ppm, see also ref. [34]). With exception of this ion, the chemical shifts of all other diperoxido complexes are below –700 ppm, in a relatively narrow range from –714 to – 749 ppm.

The range of the chemical shifts for monoperoxido complexes is wider (from –515 to –649 ppm) and is partially overlapped with the range for oxido complexes. The monoperoxido vanadium complexes are in aqueous solution generally much more stable than the diperoxido complexes. An extreme stability was observed for the [VO(O2)(nta)]2– species in aqueous solution: kept in our laboratory at room temperature and on daylight for many years exhibited only a slight decrease in molar absorption coefficient at 425 nm and an almost unchanged 51V

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NMR spectrum [193]. It seems that polydentate ligands stabilize the structure. This might be also the reason why monoperoxido compounds (3–4 vacant places in coordination sphere around VO(O2) group) are generally more stable than diperoxido complexes (1–2 vacant places in coordination sphere around VO(O2)2 group). Profoundly different is the chemical shift for “non-vanadyl” complex [V(O2)(tbdma)3] (159)

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which occurred in the plus region of chemical shifts [53].

[VO(O2)(pca)(pa)]·H2O

108 109

Ac ce pt e

76 77 78 79 89 90 91 103 106 107

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74

(H2en)[VO(O2)(ox)(pic)]·2H2O (H2en)[VO(O2)(ox)(pca)] [VO(O2)(pca)(bpy)] [VO(O2)(pca)(phen)] [VO(O2)(tppri2)(Hpzpri2)]·Thf [VO(O2)(Hsalhyhb)(H2O)]·H2O [VO(O2){HB(pz)3}(Hpz)] K[VO(O2)(Hheida)]·H2O K[VO(O2)(ada)]·4H2O [VO(O2)(bpg)]·H2O

422 [320]a 428 [294]a 452 [288]h

474 [505]d,t 477 [585]d,t 495 [280]e 490d 430 [300]a 428 [430]a,o 422 [270] and 444 [360]k,l, 448 [350] c 438 [390]a 438, pH 1.1 to 4.9

Cs[VO(O2)(ceidaa)]·H2O K[VO(O2)(ceidaa)]·2H2O

116 117 126

K[VO(O2)(omeida)]·H2O K[VO(O2)(Hheida)]·2H2O [VO(O2)(Hbpa)]2(ClO4)2·[VO(O2)(bpa)]·2.25H2O

157

PPh4[VO2(Ph3SiO)2]x[VO(O2)(Ph3SiO)2]1–x (x = 0,57) [V(O2)(tbdma)3]

159

–714 –744

–749 b,o

–744 b,o –743,6 b,t –740,8 b,t –743 b,t –745 b,t

354 [598] a,y

d

21 22 24 25 18 59 64 69 71 72

[VO(O2)2(phen)]– K2[VO(O2)2(pic)]·2H2O K2[VO(O2)2(OHpic)]·3H2O K3[VO(O2)2(2,4-pdc)]·3.25H2O K3[VO(O2)2(3-acetpic)]·2H2O NH4[VO(O2)2(bpy)]·4H2O (NEt4)[VO(O2)(glygly)]·1.58H2O [VO(O2)(pic)(bpy)] NH4[VO(O2)(pca)2]·2H2O K[VO(O2)(ox)(bpy)]·3H2O (NPr4)[VO(O2)(ox)(phen)]

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[VO(O2)2(bpy)]–

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18, 19, 26-30

δV (ppm)

cr

Table 7. UV-vis and 51V NMR data for structurally characterized complexes. No. Compound/complex λmax (nm) [ε (mol–1 dm3 cm–1)] K2[VO(O2)2F] 6 (Him)[VO(O2)(im)] 9

34

439 [357]a

–649 a,v –577 g –600b –615.5a,u –612.9a,u, – 555.7c,u –587 and – 600k,u –620.4k,u –604.5k,u –560d,u –562d,u –552m –551f –623g –565b –543 to – 545c –583.3a –580.5, pH 4.9 –515a,u –569 –624p, – 610r –595.3 and –596.8c +216.9g, 198.1e, +183.1x

Ref. [44]

[67,32] [201] [201] [79] [79] [80] [80] [17] [105] [201] [111] [113] [113] [114] [116] [116] [106] [106] [52] [122] [123] [134] [137] [14] [138] [139] [144] [115] [115] [58] [53]

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a

– in H2O; b – in D2O; c – in CH3CN or CD3CN; d – in CH2Cl2 or CD2Cl2; e – in toluene; f – in CD3OD; g – in CDCl3; h – in water-dimethylformamide (9 : 1 by vol.), pH 1.5 (by 1.0 mol/L HCl), 20 °C; i – in aqueous solution: CH3COONa-HCl, I = 1.0 mol/L (KCl), pH 3.08, 30 °C; j – in 0.1 mol/L KCl(aq); k – undergoes decomposition on dissolution; l – in an aqueous solution of HClO4; m – in C6D6; n – in aqueous solution of HClO4, I = 1.0 mol/dm3 (NaClO4), pH 4.51, 30 °C; o – data based on in situ measurements; p – in H2O-D2O; r – in D2O-C2H5OH; s – in solid state; t – at room temperature; u – at 5 °C; v – at 3 °C; x – in pentane, y – pH = 7.5.

Density functional theory (DFT) calculations provided methods for calculation of

51

V NMR

chemical shifts (Table 8). Interesting study on medium effects on 51V NMR chemical shifts of

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[VO(O2)2(H2O)]− highlighted the importance of solvation effect in hydration sphere around the anion [202]. In cases, where hybrid functionals (B3LYP, B3PW91) combined with

employed; the experimental

51

cr

medium all-electron basis sets (Wachters for V atom and IGLO-II for ligand atoms) were V NMR chemical shifts are well reproduced by the calculated

us

ones. Important remark has to be addressed here: as the 51V NMR chemical shift range is over 4000 ppm [202, 203], a calculated value differing from the experimental one by 20 ppm is

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within the error of 0.5 %.

Ac ce pt e

d

M

Table 8. Experimental and computed 51V chemical shifts in ppm relative to VOCl3 for peroxidovanadium compounds Methoda Experimenta Computed Species Ref. Basis set (for V atom and ligands) l value value GIAO-B3LYP [VO(O2)2(H2O)]− d −692 −655 [202] Wachters and 6-31++G(d) 2− [VO(O2)2F] −714.0 −722.2 GIAO-B3PW91 [98] [V2O2(O2)3F3]3− −685.0 −684.3 Wachters and IGLO-II 3− d [V2O2(O2)2F5] −672.0 −653.0 GIAO-B3LYP [V2O2(O2)2(gly)2]2− −582.8 −584.4 [165] Wachters+f and IGLO-II 2− [V2O2(O2)2(gly)2] −582.8 −424.9 [V2O3(O2)(gly)2]2− d −580.4b −436.1b UDFT-IGLO-PW91 [204] 9s7p4d (extended AVTZ) and IGLO-II [VO(O2)H2O(gly)2]2− d −574.0 −421.4 +d [VO(O2)(H2O)3] −536.3 −412.6 cis-[V2O3(O2)(L-lact)2]2− d −592.2b −433.4b trans-[V2O3(O2)(L-lact)2]2− d −590.6b −421.5b UDFT-IGLO-PW91 [206] 2− 9s7p4d (extended AVTZ) and IGLO-II [V2O2(O2)2(L-lact)2] −595.9 −421.9 −d [VO(O2)(L-lact)(H2O)] −546.0 −408.7 [VO(O2)2(H2O) ]−·(gly-L−752.0 −784.02 his)c,d − GIAO-B3LYP-PCM(D2O) [VO(O2)2(H2O)] ·(gly-gly-L[205] −754.0 −784.93 LANL2DZ and 6-31+G(d) his)c,d [VO(O2)2(H2O) ]−·(gly-L-his−748.0 −786.18 gly)c,d a Equilibrium geometries were optimized at the DFT level in the gas-phase [203, 98, 165, 204, 205, 206] or additionally using Car-Parrinello molecular dynamics to include zero-point, temperature and solvent effects [202]. For complete experimental and computational details see the references. b The compounds are composed of dioxido and oxido-peroxido moieties. The reported values correspond to the oxido-peroxido centers. c Peptide adducts. d No X-ray structure is available.

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In this context, there are some studies devoted to the simulation of reaction pathways of vanadium-catalyzed oxidation reactions in the presence of hydrogen peroxide and thus involving peroxidovanadium compounds. The combination of quantum chemical calculations and speciation data obtained mainly by

51

V NMR spectroscopy provided some clues on the

reaction mechanisms. The extensive topic of (peroxido)vanadium-catalyzed reactions is covered in other reviews [11, 22, 24, 206,207, 208] and we have included some general

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considerations which deserve more attention and directly involve peroxido complexes of

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d

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vanadium in the section 9 Outlook and Perspectives.

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9 Outlook and perspectives

In our review, we focused on synthesis, structure, spectral properties and thermal decomposition of peroxido complexes of vanadium(V), while the excellent reviews referenced in Introduction shed some light on their reactivity and practical applications. Concurrently with the rapidly increased number of diverse structurally characterized peroxido

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complexes of vanadium goes the introduction of advanced protocols for vanadium catalyzed oxidations with hydrogen peroxide and the tremendous progress in bioinorganic chemistry of

cr

vanadium. It may seem that the chemistry of peroxidovanadates is at the edge of its development. One may also notice that the number of scientific articles dealing with

us

peroxidovanadates has in recent years slightly decreased; however, the scope of applications of peroxidovanadates is broadening. The initial interest in medicinal applications of

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peroxidovanadates (e.g. insulin mimetics) has been partially ceased because of the predominance of their negative side effects (mainly instability under physiological conditions, toxicity of vanadium, possible release of the peroxido ligand and mucous membrane burns,

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availability of safer analogues) over advantages.

The role of peroxidovanadates in vanadium catalyzed oxidations in the presence of hydrogen

d

peroxide can be considered as their main practical application. It is thus quite surprising that

Ac ce pt e

in many cases the catalytic reaction is performed by simple mixing of the substrate, vanadium source and ligands, without any speciation study and structural characterization of the genuine catalytic species. We have already emphasized that the composition of peroxidovanadates in organic solvents should be much further studied to understand the catalytic processes. The lack of data on composition of catalytic systems makes it also impossible to review thoroughly the structure of peroxidovanadates in solutions. During recent decades several works aimed at the elucidation of the composition of catalytic systems have appeared, which pointed to the presence of some peroxidovanadium complexes in reaction mixtures composed of a substrate, vanadium source, ligands and hydrogen peroxide in organic solvents [41, 42, 209]. 51V NMR spectroscopy was used as the main tool for this purpose, but this method does not allow to determine the structure of the real catalytically active particle which remains in the vast majority of cases still elusive. An interesting challenge lies in indications that a hydrogenperoxidovanadium complex may be formed during catalytic reactions. In model systems it was reported that for the activity of vanadium-peroxidase systems the addition of a strong acid is required [210, 211, 212, 213, 214]. This proposal was supported by several DFT calculations [210]. However, except of 37

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special cases of compounds 53 and 54, there is no hydrogenperoxido complex known in solid state and no

51

V NMR speciation study confirmed or at least proposed existence of such

complexes. Therefore, it is of utmost importance to take a closer look at the mechanism of vanadium catalyzed oxidation and to introduce advanced experimental and theoretical methods in order to illuminate the reactivity of vanadium peroxido complexes in the most promising area of their practical application.

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One of the promising applications of peroxidovanadates that deserves much more attention is the use of peroxidovanadates as precursors for the synthesis of large vanadium clusters,

cr

especially polyoxometalates. The formation of decavanadates by the peroxide route was already studied [215, 216, 217]. Dissolution of V2O5 in diluted hydrogen peroxide solution

us

and the subsequent spontaneous decomposition of the resulting peroxido complexes of vanadium leads to the formation of decavanadate, which upon reacting with H3PO4 gives

an

(HxPV14O42)(9−x)− [218, 219, 220]. The reaction of this heteropolyvanadate with MoVI precursors (e.g. MoO3) results in several Mo-V-P heteropolyoxometalates with the general formula H3+xPMo12–xVxO40. The synthetic strategy is summarized in the following reaction

M

steps:

V2O5 + H2O2 → peroxido complexes of vanadium → HxV10O28(6−x)−

2.

HxV10O28(6−x)− + H3PO4 → (HxPV14O42)(9−x)− + H2O

3.

(HxPV14O42)(9−x)− + MoO3 + H3PO4 + H2O → H3+xPMo12-xVxO40

Ac ce pt e

d

1.

Modification of the synthesis may lead to the formation of larger clusters HaPzMoyVxOb [218]. Although the role of H2O2 in the whole synthesis procedure may seem marginal it has to be pointed out that the analogical activation of V2O5 into the peroxidovanadate intermediates and subsequent multistep reactions (without the substep formation of decavanadate) lead to the formation of fluorinated dodecavanadate [V12O30F4(H2O)2]4− ilustrating the great potential of the peroxidovanadate-mediated synthesis of polyoxometalates [221]. Additionally, this route offers the exclusive option to choose freely the counter ion and the possible heteroatoms of the polyoxometalate. More generally, the method utilizing peroxidic species may become very important for the synthesis of novel materials [222, 223]. The peroxido complexes of vanadium are particularly suitable for the synthesis of transition metal vanadates by thermal decomposition. The peroxidovanadates can be crystallized as relatively pure solids allowing the preparation of interesting materials of exceptionally high purity. Also the temperature required for the 38

Page 38 of 46

release of the peroxido oxygen atoms and of eventual heteroligands may be as low as several hundreds of °C. Cu(VO3)2, Zn(VO3)2 [69] and Ni2V2O7 [70] are the examples of compounds prepared by this method (Section 6). Another possibility is the use of peroxido complexes of early transition metals as precursors of heterometallic materials suitable for catalysis. Various dopants, including vanadium [224, 225], are used to enhance catalytic and photocatalytic

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activity of prepared materials.

Ac ce pt e

d

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Table 9. Abbreviations used (not explained in Table 2 and Scheme 2). Abbreviation Explanation bpbp 2,6-bis{[N,N-bis(2-pyridylmethyl)amino]methyl}-4-tert-butylphenolato(1–) bpz*eaT 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-diethylamino-1,3,5-triazine cym 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane en ethane-1,2-diamine gdn guanidine gly-gly-L-his glycylglycyl-L-histidine tripeptide gly-L-his glycyl-L-histidine dipeptide gly-L-his-gly glycyl-L-histidylglycine tripeptide Hpan 1-(2-pyridylazo)-2-naphthol L1 hydrotris(3,5-diisopropylpyrazol-1-yl)borate(1–) L2 3,5-diisopropylpyrazole Lax axial ligand (trans to the oxido ligand) L-N4Me2 N,N’-dimethyl-2,11-diaza[3.3](2,6)pyridinophane NBu4 tetrabutylammonium cation NEt4 tetraethylammonium cation nica nicotinamide NMe4 tetramethylammonium cation NPr4 tetrapropylammonium cation Op peroxido oxygen atom PPh4 tetraphenylphosphonium cation py pyridine 4,4’-tBu2bpy 4,4’-di-tert-butyl-2,2’-bipyridine tbdma N-tert-butyl-3,5-dimethylaniline(1–) tpa tris(2-pyridylmethylamine) tren tris(2-aminoethyl)amine XPD X-ray powder diffraction

Acknowledgements

We are indebted to Associate Professor Michal Sivák, for critical reading of the manuscript and valuable remarks. This work was supported by the Grant Agency of the Ministry of Education of the Slovak Republic and Slovak Academy of Sciences VEGA Project 1/0336/13.

Highlights Structures of 163 peroxido complexes of vanadium are reviewed Structural aspects and reactivity in solution are discussed Vibrational spectra, 51V NMR spectra and thermal decomposition data are provided Future development of peroxidovanadium compounds is proposed

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References

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